Inks comprising linear ABSCS′B′A′or BASCS′A′B′alkylene oxide/siloxane block copolymers

ABSTRACT

Disclosed is an ink composition comprising water, a colorant, and an ABSCS′B′A′ or BASCS′A′B′ block copolymer wherein A and A′ are blocks containing one or more ethylene oxide repeat monomer units, B and B′ are blocks containing one or more propylene oxide repeat monomer units, C is a block comprising one or more repeat monomer units of an alkylsiloxane, a dialkylsiloxane, an alkyl aryl siloxane, or a diarylsiloxane, S is an optional spacer group between the A or B block and the C block, and S′ is an optional spacer group between the C block and the A′ or B′ block. Also disclosed is a multicolor ink jet printing process using the ink, wherein dry time is reduced and/or intercolor bleed is reduced.

Cross-reference is made to copending application U.S. Ser. No. U.S. Ser.No. 09/776,515, filed concurrently herewith, entitled “Inks ComprisingLinear ASBS′A′ Block Copolymers of Alkylene Oxide and Siloxane,” withthe named inventor John Wei-Ping Lin, the disclosure of which is totallyincorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention is directed to ink compositions and ink jetprinting processes. More specifically, the present invention is directedto aqueous ink compositions particularly suitable for the production ofhigh quality images on print substrates. One embodiment of the presentinvention is directed to an ink composition comprising water, acolorant, and an ABSCS′B′A′ or BASCS′A′B′ block copolymer wherein A andA′ are blocks containing one or more ethylene oxide repeat monomerunits, B and B′ are blocks containing one or more propylene oxide repeatmonomer units, C is a block comprising one or more repeat monomer unitsof an alkylsiloxane, a dialkylsiloxane, an alkyl aryl siloxane, or adiarylsiloxane, S is an optional spacer group between the A or B blockand the C block, and S′ is an optional spacer group between the C blockand the A′ or B′ block. Another embodiment of the present invention isdirected to a set of inks for printing multicolor images in an ink jetprinter, said ink set comprising (1) a first ink having a first colorand comprising water and a first colorant; and (2) a second ink having asecond color different from the first color and comprising water, acolorant, and an ABSCS′B′A′ or BASCS′A′B′ block copolymer wherein A andA′ are blocks containing one or more ethylene oxide repeat monomerunits, B and B′ are blocks containing one or more propylene oxide repeatmonomer units, C is a block comprising one or more repeat monomer unitsof an alkylsiloxane, a dialkylsiloxane, an alkyl aryl siloxane, or adiarylsiloxane, S is an optional spacer group between the A or B blockand the C block, and S′ is an optional spacer group between the C blockand the A′ or B′ block, wherein dry time of the ink containing the blockcopolymer is decreased and/or intercolor bleed between the first ink andthe second ink is reduced when the second ink is printed adjacent to, ontop of, or underneath the first ink on a print substrate. Yet anotherembodiment of the present invention is directed to a multicolor ink jetprinting process which comprises: (1) incorporating into an ink jetprinter a first ink having a first color and comprising water and afirst colorant; (2) incorporating into the ink jet printer a second inkhaving a second color different from the first color and comprisingwater, a colorant, and an ABSCS′B′A′ or BASCS′A′B′ block copolymerwherein A and A′ are blocks containing one or more ethylene oxide repeatmonomer units, B and B′ are blocks containing one or more propyleneoxide repeat monomer units, C is a block comprising one or more repeatmonomer units of an alkylsiloxane, a dialkylsiloxane, an alkyl arylsiloxane, or a diarylsiloxane, S is an optional spacer group between theA or B block and the C block, and S′ is an optional spacer group betweenthe C block and the A′ or B′ block; (3) causing droplets of the firstink to be ejected in an imagewise pattern onto a substrate; and (4)causing droplets of the second ink to be ejected in an imagewise patternonto the substrate, wherein dry time of the ink containing the blockcopolymer is decreased and/or intercolor bleed between the first ink andthe second ink is reduced when the second ink is printed adjacent to, ontop of, or underneath the first ink on the substrate.

Ink jet printing is a non-impact printing method which produces dropletsof ink that are deposited on a print substrate in response to electronicdigital data signals. Ink jet systems generally are of two types:continuous stream and drop-on-demand. In continuous stream ink jetsystems, ink is ejected in a continuous stream under pressure through atleast one orifice or nozzle. The stream of ink is periodically perturbedby pressure regulation in accordance with digital signals, causing it tobreak up into droplets at a fixed distance from the nozzle. At thebreak-up point, the charged ink droplets pass through an electricalfield which adjusts the trajectory of each ink droplet to direct it to agutter for ink circulation or to a specific location on a printsubstrate to produce an image. In a drop-on-demand system, an inkdroplet is expelled from a nozzle directly onto a print substrate inaccordance with digital data signals. Generally, a droplet is not formedor expelled unless it is to be placed on a print substrate.

Drop-on-demand systems are simpler than continuous stream systems sincethey do not require ink recovery, charging, or deflection. There arethree types of drop-on-demand ink jet systems. One type ofdrop-on-demand system has an ink-filled channel or passageway having anozzle on one end and a piezoelectric transducer near the other end toproduce pressure pulses according to digital data signals. Multiple inknozzles are used to deliver ink droplets onto a print substrate in animagewise fashion. Several printheads and inks are used in a multicolorpiezoelectric ink jet printing system. High resolution images can beobtained with this system. Examples of this system include the Epson600, 800, and 1200 Ink Jet printers.

Another type of drop-on-demand ink jet printing system is calledacoustic ink jet printing, which can be operated at high frequency andhigh resolution. Acoustic ink jet printing uses a focused acoustic beamformed with a spherical lens illuminated by a plane wave of soundcreated by a piezoelectric transducer. The focused beam reflected from asurface exerts a pressure onto the surface of the liquid ink, resultingin ejection of small droplets of ink onto a print substrate. An array ofnozzles and corresponding transducers are used in an acoustic ink jetprinting process to produce images on a print substrate in an imagewisefashion. Different types and configurations of acoustic printheads andsubstrate arrangements are possible. In a multicolor ink jet printingprocess, several acoustic ink jet printheads are used to deliverdifferent inks onto a print substrate. Aqueous inks can be used in thisdrop-on-demand acoustic ink jet printing system. Examples of acousticink jet printing systems are disclosed in, for example K. A. Krause,“Focusing Ink Jet Head,” IBM Technical Disclosure Bulletin, Vol 16, No.4, September 1973, pp. 1168-1170, and in, for example, U.S. Pat. Nos.4,308,547, 4,697,195, 5,028,937, 5,041,849, 4,751,529, 4,751,530,4,751,534, 4,801,953, and 4,797,693, the disclosures of each of whichare totally incorporated herein by reference. The use of focusedacoustic beams to eject droplets of controlled diameter and velocityfrom a free-liquid surface is also described in J. Appl. Phys., vol. 65,no. 9 (May 1, 1989) and references therein, the disclosure of which istotally incorporated herein by reference.

Another type of drop-on-demand printing system is thermal ink jetprinting. Thermal or bubble jet drop-on-demand ink jet printers havefound broad applications as output for personal computers in the officeand in the home. In thermal ink jet printing processes, the printheadtypically comprises one or more ink jet ejectors, as disclosed in, forexample, U.S. Pat. Nos. 4,601,777, 4,532,530, 4,412,224, 4,410,899,4,251,824, 4,532,530, 4,601,777, 4,840,674, 5,145,518, 5,281,261, and5,531,818, the disclosures of each of which are totally incorporatedherein by reference. Each ejector includes a channel communicating withan ink supply chamber, or manifold, at one end and an opening at theopposite end, referred to as a nozzle. A thermal energy generator,usually a resistor, is located in each of the channels at apredetermined distance from the nozzles. The resistors are individuallyaddressed with a current pulse to vaporize the ink momentarily withinthe respective channel to form a bubble that expels an ink droplet. Asthe bubble grows, the ink rapidly bulges from the nozzle and ismomentarily contained by the surface tension of the ink as a meniscus.This phenomenon is temporary, and the ink is quickly propelled toward aprint substrate. As the bubble begins to collapse, the ink still in thechannel between the nozzle and the bubble starts to move towards thecollapsing bubble, causing a volumetric contraction of the ink at thenozzle and resulting in the separation from the nozzle of the bulgingink as a droplet. The acceleration of the ink out of the nozzle whilethe bubble is growing provides the momentum and velocity for propellingthe ink droplet in a substantially straight direction toward a printsubstrate, such as a piece of paper, transparency, textile, or the like.Some important properties of the ink in this context include desirableviscosity and surface tension, adequate drop velocity, good latency andfrequency response, minimum heater deposits (kogation), and no softthreshold voltage problems. Because the droplet of ink is emitted onlywhen the resistor is actuated, thermal ink jet printing is adrop-on-demand system.

In a drop-on-demand ink jet printing apparatus, the printhead typicallycomprises a linear array of ejectors, and the printhead (with or withoutpartition) is moved relative to the surface of the print substrate,either by moving the print substrate relative to a stationary printhead,or vice versa, or both. In some apparatus, a relatively small printheadmoves across a print substrate numerous times in swaths (i.e., multiplepasses) to print a desired image. In this instance, the desired image isproduced completely on a print substrate in several swaths before thesubstrate is advanced. This type of printing is called multi-pass(multiple pass) or checkerboard ink jet printing. In checkerboard inkjet printing (or multiple pass), the printhead passes over the printsubstrate and provides ink at desired locations (for example, printingonly even or odd numbered dots in a swath). On one or more subsequentpasses, the remaining dots in the image are printed before the printsubstrate is advanced. Multiple ink jet printheads and ink cartridgescan be used to produce multiple color images on a print substrate.Alternatively, a printhead (partial width printhead or partitionedprinthead) can be partitioned into several sections (for example, threesmall sections including cyan, magenta, and yellow inks, or four smallsections including cyan, magenta, yellow, and black inks) and equippedwith different ink chambers, ink storage media, and inks in a multicolorink jet printing system. These multicolor systems are commonly employedin desktop ink jet printers, including thermal ink jet printers andpiezoelectric ink jet printers. They produce good multicolor images onprint substrates such as plain papers and transparencies, but at aslower printing speed. Slightly higher printing speed can be achieved,however, by increasing ink jetting frequency and printhead sweeping rateas well as by using multiple printheads (without partition) and inks.

The ink jet printing apparatus can also employ a printhead comprisingtwo or more printheads butted together to cover a larger width of theprint substrate (butted printhead). This type of partial width printheadhas more ink nozzles per printhead and can deliver more ink in eachswath across the print substrate. In the multi-pass (multiple passes) orcheckerboard ink jet printing process a faster ink jet printing processcan be carried out. Multicolor ink jet printing processes can useseveral butted ink jet printheads (e.g. for black, cyan, magenta, andyellow inks) in an ink jet printer to produce multicolored images onsubstrates at a faster rate than processes using several regular singleprintheads without butting (unbutted printheads).

Alternatively, a stationary ink jet printhead that consists of an arrayof ejectors and extends the full width of a print substrate (full widtharray printhead) can pass ink down the print substrate to give full pageimages, in what is known as a “full width array” ink jet printer. Whenthe printhead and the print substrate are moved relative to each other,imagewise digital data is used to activate the thermal energy generatorsor resistors selectively in the printhead over time so that the desiredimage can be created quickly on the print substrate in a single passmode. The full width array printhead is generally preferred to be in astationary position while the print substrate is continuously moving toreceive inks as it passes through the printhead or printheads. The fullwidth array printhead or printheads can also, however, be moved acrossthe print substrate if desired. In a multicolor ink jet printingprocess, several full width array printheads, including cyan, magenta,yellow, and black printheads, as well as other optional printheads andtheir corresponding inks, can be used to provide different coloredimages on the print substrate at a high speed. Fast ink jet printing canbe achieved by using the full width array printheads.

In a multicolor ink jet printing process, several inks can be printed ona print substrate. In some instances two different inks can be printednext to each other. Intercolor bleed can occur if the inks are not driedproperly or if the printing process is too fast for the ink set.Undesired ink mixing on a print substrate, especially on the surface ofa plain paper, can cause severely distorted images near the border oftwo inks. After ink drying, the border of the two inks shows irregularstructure with poor edge sharpness (or raggedness) because of theinvasion of one ink into the other. The bleed images are not desirableand can be detected easily by eyes. This phenomenon is called intercolorbleed or color bleed. Intercolor bleed is particularly noticeable when adarker ink (such as a black ink) and a lighter ink (such as a yellowink, a cyan ink, magenta ink, or the like) are printed next to eachother, because of high contrast between the two colors. Intercolor bleedcan also occur when two color inks are printed next to each other (forexample, a yellow ink next to a magenta ink, a yellow ink next to a cyanink, a magenta ink next to a cyan ink, or the like). The severity of theintercolor bleed generally is affected by ink type and composition,absorption rate of the printed substrate, printhead design, ink dropmass, ink dot size, and method and speed of printing. There is a need toreduce or minimize intercolor bleed and dry time and to produce highquality multicolor ink jet images on print substrates, including plainand coated papers, transparencies, textiles, and other desiredsubstrates.

While known compositions and processes are suitable for their intendedpurposes, a need remains for improved ink compositions. In addition, aneed remains for improved ink compositions suitable for use in ink jetprinting processes. Further, a need remains for ink sets for ink jetprinting that enable the generation of multicolored images with reducedintercolor bleed. Additionally, a need remains for ink compositions thatenable improved print quality with sharp line edges. There is also aneed for ink compositions with reduced drying time. In addition, thereis a need for ink compositions that exhibit desirable surface tensionvalues. Further, there is a need for ink compositions that generateimages with improved uniformity of solid image areas. Additionally,there is a need for ink compositions with desirable latency values inink jet printers. A need also remains for ink compositions that improveink jet printhead maintainability. In addition, a need remains formulticolor ink jet printing processes that enable desirable printquality and uniform solid area images.

SUMMARY OF THE INVENTION

The present invention is directed to an ink composition comprisingwater, a colorant, and an ABSCS′B′A′ or BASCS′A′B′ block copolymerwherein A and A′ are blocks containing one or more ethylene oxide repeatmonomer units, B and B′ are blocks containing one or more propyleneoxide repeat monomer units, C is a block comprising one or more repeatmonomer units of an alkylsiloxane, a dialkylsiloxane, an alkyl arylsiloxane, or a diarylsiloxane, S is an optional spacer group between theA or B block and the C block, and S′ is an optional spacer group betweenthe C block and the A′ or B′ block. Another embodiment of the presentinvention is directed to a set of inks for printing multicolor images inan ink jet printer, said ink set comprising (1) a first ink having afirst color and comprising water and a first colorant; and (2) a secondink having a second color different from the first color and comprisingwater, a colorant, and an ABSCS′B′A′ or BASCS′A′B′ block copolymerwherein A and A′ are blocks containing one or more ethylene oxide repeatmonomer units, B and B′ are blocks containing one or more propyleneoxide repeat monomer units, C is a block comprising one or more repeatmonomer units of an alkylsiloxane, a dialkylsiloxane, an alkyl arylsiloxane, or a diarylsiloxane, S is an optional spacer group between theA or B block and the C block, and S′ is an optional spacer group betweenthe C block and the A′ or B′ block, wherein dry time of the inkcontaining the block copolymer is decreased and/or intercolor bleedbetween the first ink and the second ink is reduced when the second inkis printed adjacent to, on top of, or underneath the first ink on aprint substrate. Yet another embodiment of the present invention isdirected to a multicolor ink jet printing process which comprises: (1)incorporating into an ink jet printer a first ink having a first colorand comprising water and a first colorant; (2) incorporating into theink jet printer a second ink having a second color different from thefirst color and comprising water, a colorant, and an ABSCS′B′A′ orBASCS′A′B′ block copolymer wherein A and A′ are blocks containing one ormore ethylene oxide repeat monomer units, B and B′ are blocks containingone or more propylene oxide repeat monomer units, C is a blockcomprising one or more repeat monomer units of an alkylsiloxane, adialkylsiloxane, an alkyl aryl siloxane, or a diarylsiloxane, S is anoptional spacer group between the A or B block and the C block, and S′is an optional spacer group between the C block and the A′ or B′ block;(3) causing droplets of the first ink to be ejected in an imagewisepattern onto a substrate; and (4) causing droplets of the second ink tobe ejected in an imagewise pattern onto the substrate, wherein dry timeof the ink containing the block copolymer is decreased and/or intercolorbleed between the first ink and the second ink is reduced when thesecond ink is printed adjacent to, on top of, or underneath the firstink on the substrate.

DETAILED DESCRIPTION OF THE INVENTION

The ink compositions of the present invention comprise an aqueous liquidmedium, a colorant, and a block copolymer. The aqueous liquid medium canconsist solely of water, or can also include water soluble or watermiscible organic components such as humectants, cosolvents, and thelike. Many useful known humectants and/or cosolvents are suitable foruse in the inks for the present invention. Some suitable humectants andcosolvents include, but are not limited to, glycol derivatives, such asethylene glycol, diethylene glycol, propylene glycol, dipropyleneglycol, polyethylene glycol, polypropylene glycol,poly(ethylene-co-propylene) glycol, and the like, as well as theirreaction products with alkylene oxides, including ethylene oxide andpropylene oxide; alkyl ethers of glycol derivatives, such as alkylethers (alkyl group containing from about 1 to 25 carbon atoms) ofethylene glycol, diethylene glycol, propylene glycol, dipropyleneglycol, poly ethylene glycol, polypropylene glycol,poly(ethylene-co-propylene) glycol, and the like; triol derivativescontaining from about 3 to about 40 carbon atoms, including glycerine,trimethylolpropane, 1,3,5-pentanetriol, 1,2,6-hexanetriol, and the like,as well as their reaction products with alkylene oxides, includingethylene oxide, propylene oxide, and mixtures thereof; diols containingfrom about 2 to about 40 carbon atoms, such as 1,3-pentanediol,1,4-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,6-hexanediol,1,5-hexanediol, 2,6-hexanediol, neopentyl glycol(2,2-dimethyl-1,3-propanediol), and the like, as well as their reactionproducts with alkylene oxides, including ethylene oxide and propyleneoxide in any desirable molar ratio to form materials with a wide rangeof molecular weights; sulfoxide derivatives containing from about 2 toabout 40 carbon atoms, including dialkylsulfoxides (symmetric andasymmetric sulfoxides) such as dimethylsulfoxide, methylethylsulfoxide,alkylphenyl sulfoxides, and the like; sulfone derivatives (symmetric andasymmetric sulfones) containing from about 2 to about 40 carbon atoms,including dialkyl sulfones such as dimethysulfone, methylethylsulfone,diethylsulfone, ethylpropylsulfone, dipropylsulfone, propylbutylsulfone,dibutylsulfone, sulfolane (tetramethylenesulfone, a cyclic sulfone),methylsulfolane, dimethylsulfolane, and the like, alkyl phenyl sulfones,such as methylphenylsulfone, ethylphenyl sulfone, and the like; amideswith from about 2 to about 40 carbon atoms, such as N-alkylamides,N,N-dialkyl amides, N,N-alkyl phenyl amides, 2-pyrrolidinone (a cyclicamide), N-methylpyrrolidinone (a cyclic amide),N-cyclohexylpyrrolidinone, N,N-dimethyl-p-toluamide (aromatic),N,N-dimethyl-o-toluamide, N,N-diethyl-m-toluamide, and the like; ethers,such as alkyl ether derivatives of various alcohols, ether derivativesof triols and diols, including butylcarbitol, hexylcarbitol,triolethers, alkyl ethers of polyethyleneglycols, alkyl ethers ofpolypropyleneglycols, phenyl ethers of polyethyleneglycols, phenylethers of polypropyleneglycols, alkyl ethers ofphenylpolyethyleneglycols, alkyl ethers of phenylpolypropyleneglycols,and the like; urea and urea derivatives; inner salts such as betaine,and the like; thio (sulfur) derivatives (or isomers) of theaforementioned materials (humectants), including thioethyleneglycol,thiodiethyleneglycol, trithio- or dithio-diethyleneglycol, and the like;hydroxyamide derivatives, including acetylethanolamine,acetylpropanolamine, propylcarboxyethanolamine,propylcarboxypropanolamine, and the like; reaction products ofaforementioned materials (humectants) with alkylene oxides; and mixturesthereof.

Further examples of suitable humectants are disclosed in, for example,U.S. Pat. Nos. 5,281,261, 5,531,818, 5,693,129, 4,840,674, 5,356,464,copending application U.S. Ser. No. 08/782,237, and copendingapplication U.S. Ser. No. 08/876,41, the disclosures of each of whichare totally incorporated herein by reference. For example, U.S. Pat. No.5,693,129 discloses the use of hydroxyamide derivatives, mercaptoamidederivatives, hydroxythioamide derivatives, mercaptothioamidederivatives, and oxyalkylene (alkyleneoxide) reaction products of theabove said derivatives as anticurl agents for ink jet ink compositions.These materials and other known anti-curl agents, including thosedisclosed in, for example, U.S. Pat. No. 5,356,464 can be employed inthe inks for the present invention to provide both anticurl andantibleed properties for the production of multicolor images.Furthermore, ink compositions for the present invention furthercomprising some of the materials disclosed in U.S. Pat. No. 5,693,129and copending application U.S. Ser. No. 08/782,237 can be used in a highresolution ink jet printing process to provide long ink latency and highfrequency response. The inks for the present invention, in someembodiments, will have a reduced tendency to clog the printhead nozzlesor resist smooth ink flow, and will exhibit less frequency of inkspitting and printhead wiping for maintenance. Furthermore, the inkcompositions for the present invention can be used with regularprintheads, partitioned printheads, partial width printheads, and fullwidth array printheads in ink jet printing processes. The ability of theink compositions for the present invention to be jetted at highfrequency (because of high frequency response, typically 3 KiloHertz orgreater) allows one to print multicolor ink jet images at high speed,especially when full width array ink jet printheads are used. A printingspeed of 50 copies per minutes for the production of multicolor imagescan be achieved using a set of full width array printheads (e.g. black,cyan, magenta, and yellow). The print substrates can optionally beheated at any stage of the printing process, including before, during,and after the printing process as well as combinations thereof.

Humectants, if present, are in the ink in any desired or effectiveamount, typically up to about 45 percent by weight of the ink,preferably up to about 40 percent by weight of the ink, and morepreferably from about 5 to about 35 percent by weight of the ink,although the amount can be outside of these ranges.

Ink compositions of the present invention can also be prepared with lowviscosity. Low molecular weight materials are preferred in the inks.Some examples of additional useful ink ingredients are disclosed in, forexample, U.S. Pat. Nos. 5,281,261, 5,531,818, and 5,693,129, thedisclosures of each of which are totally incorporated herein byreference. Ink compositions for the present invention with low viscositycan allow fast ink jetting and refill in multicolor ink jet printingprocesses with inks of the present invention. The viscosity of the inkcomposition is usually less than about 20 centipoise (at roomtemperature, i.e., about 25° C.), preferably from about 1 to about 10centipoise, and more preferably from about 1 to about 5 centipoise.

The ink compositions of the present invention further contain acolorant. The colorant can be a pigment, a dye, or a mixture thereof. Apigment colorant is one that is substantially insoluble in the inkaqueous medium. The pigment can be selected from the suitable colorantslisted in the Color Index, published jointly by American Association ofTextile Chemist and Colorists (AATCC) and The Society of Dyers andColorists in Bradford, England; BUYER'S GUIDE for Textile Chemist andColorist, published by AATCC, and the like. The pigment can be presentin the inks either with or without a dispersing agent. For example,pigment particles such as those modified chemically to possess waterionizable functional groups (either negatively or positively charged),such as carboxylate, sulfonate, phosphonate, phosphate, or ammoniumgroups, are stable in an aqueous ink and do not necessarily require adispersing agent. Unlike many commercially available unmodifiedpigments, which rely primarily on external polymeric dispersants forneeded stability in aqueous inks, the chemically modified pigments havethe functional groups attached directly to the pigment particle surfacesvia covalent bonds. The water ionizable functional groups can stabilizethe pigment particles in the aqueous ink medium and provide neededstability without undesired pigment precipitation or coagulation. Ifneeded, however, a pigment dispersant can also be used in conjunctionwith the chemically modified pigment (or surface modified pigment) toimprove the stability of the ink. Some examples of chemically modifiedpigments are disclosed in, for example, U.S. Pat. No. 5,281,261, thedisclosure of which is totally incorporated herein by reference; alsosuitable are commercial carbon black dispersions such as Cabojet® 200,Cabojet® 300 (surface modified pigment), colored pigment dispersions,available from Cabot Chemical Co., the Bonjet® carbon black dispersionsfrom Orient Chemical Company of Japan, other commercially availablesurface modified pigments (e.g. carbon black and color pigments), andthe like. Pigment particles which are not chemically modified preferablyare present with at least a dispersing agent (or dispersant) tostabilize the particles in an aqueous ink. The pigment stabilizing ordispersing agent can be anionic, cationic, or nonionic.

Pigments can be of any desired color, such as black, cyan, magenta,yellow, red, blue, green, brown, or the like, as well as mixturesthereof. It is preferred that the pigment particles in an ink jet inkcomposition have the same or similar color so there is no interferenceor impairment of the desired color of the final ink. Examples ofsuitable pigments in the ink jet ink compositions include, but are notlimited to, various carbon blacks such as channel blacks; furnaceblacks; lamp blacks; Raven® carbon blacks including Raven® 5250, Raven®5750, Raven® 3500 and other similar carbon black products available fromColumbia Company; carbon blacks including Regal® 330, Black Pearl® L,Black Pearl® 1300, and other similar carbon black products availablefrom Cabot Corporation; Degussa carbon blacks such as Color Black®series, Special Black® series, Printtex® series and Derussol® carbonblack dispersions available from Degussa Company; Cabojet® series carbonblack dispersions including Cabojet® 200, Cabojet® 300, Cabojet® IJX157, Cabojet® IJX 164, and the like from Cabot corporation; Lavanyl®carbon black dispersions from Bayer Company, Special Black® carbon blackdispersions from BASF Co.; Hostafine® series pigment dispersions such asHostafine® Yellow GR (Pigment 13), Hostafine® Yellow (Pigment 83),Hostafine® Red FRLL (Pigment Red 9), Hostafine® Rubine F6B (Pigment184), Hostafine® Blue 2G (Pigment Blue 15:3), Hostafine® Black T(Pigment Black 7, carbon black), and Hostafine® Black TS (Pigment Black7), available from Hoechst/Celanese Corporation; Normandy MagentaRD-2400 (Paul Uhlich); Paliogen Violet 5100 (BASF); Paliogen® Violet5890 (BASF) Permanent Violet VT2645 (Paul Uhlich); Heliogen Green L8730(BASF); Argyle Green XP-111-S (Paul Uhlich); Brilliant Green Toner GR0991 (Paul Uhlich); Heliogen® Blue L6900; L7020 (BASF), Heliogen® BlueD6840, D7080 (BASF); Sudan Blue OS (BASF); PV Fast Blue B2G01(Hoechst/Celanese); Irgalite Blue BCA (Ciba-Geigy); Paliogen® Blue 6470(BASF); Sudan III (Matheson, Coleman, Bell); Sudan II (Matheson,Coleman, Bell); Sudan IV (Matheson, Coleman, Bell); Sudan Orange G(Aldrich); Sudan Orange 220 (BASF); Paliogen® Orange 3040 (BASF); OrthoOrange OR 2673 (Paul Uhlich); Paliogen® Yellow 152, 1560 (BASF); LitholFast Yellow 0991 K (BASF); Paliotol Yellow 1840 (BASF); Novoperm® YellowFG 1 (Hoechst/Celanese); Permanent Yellow YE 0305 (Paul Uhlich); LumogenYellow D0790 (BASF); Suco-Gelb L1250 (BASF); Suco-Yellow D1355 (BASF);Hostaperm® Pink E (Hoechst/Celanese), Fanal Pink D4830 (BASF); CinquasiaMagenta (DuPont); Lithol Scarlet D3700 (BASF); Toluidine Red (Aldrich);Scarlet for Thermoplast NSD PS PA (Ugine Kuhlmann of Canada); E. D.Toluidine Red (Aldrich); Lithol Rubine Toner (Paul Uhlich); LitholScarlet 4440 (BASF); Bon Red C (Dominion Color Company); Royal BrilliantRed RD-8192 (Paul Uhlich); Oracet Pink RF (Ciba-Geigy); Pigment Red 122from Toyo Ink of Japan; Paliogen® Red 3871 K (BASF); Paliogen® Red 3340(BASF); Lithol Fast Scarlet L4300 (BASF); and mixtures thereof. Manyuseful pigments can also be found in the Color Index, published jointlyby American Association of Textile Chemist and Colorists (AATCC) and TheSociety of Dyers and Colorists in Bradford, England.

Pigment colorants can be present in the ink in any effective amount.Typically the pigment is present in an amount of from about 0.1 to about15 percent by weight of the ink, and preferably from about 1 to about 10percent by weight of the ink, although the amount can be outside ofthese ranges.

Preferably, the pigment particle size is as small as possible to enablea stable colloidal suspension of the particles in the liquid medium withgood color strength, and to prevent clogging of the ink channels ornozzle openings when the ink is used in an ink jet printer. Preferredaverage particle sizes or diameters are generally from about 0.001 toabout 3 microns, although the particle sizes can be outside of theseranges. A more preferred pigment particle size distribution is onewherein particles having at least 50 percent of the particles beingbelow 0.3 micron, with no particles being greater than 3.0 microns(measured on, for example, a Hodaka CAPA 700 Particle Size Analyzer, aMalvern particle size analyzer, a Model BI-90 Brookhaven Instrumentsparticle size analyzer, or the like). More preferably, the averagepigment particle size includes particles having at least 70 percent ofthe particles being below 0.3 micron, with no particles being greaterthan 1.2 microns. Pigment particle sizes can, however, be outside ofthese ranges provided that they do not cause undesired clogging andmaintenance problems.

In some embodiments of the present invention, the pigment can bedispersed in the ink with one or more dispersants (dispersing agents) orstabilizing agents. The stabilizing agents can be anionic, cationic, ornonionic. Some pigment stabilizing agents have both hydrophilic(comprising ionic groups which are capable of ionizing in water or watercompatible groups) and hydrophobic (affinity for pigments) moieties.Suitable stabilizing agents include, but are not limited to, anionicdispersants, such as polymers and random copolymers of styrene sulfonatesalts (such as Na⁺, Li⁺, K⁺, Cs⁺, Rb⁺, substituted and unsubstitutedammonium cations, and the like), unsubstituted and substituted (such asalkyl, alkoxy, substituted naphthalene derivatives, and the like)naphthalene sulfonate salts (such as Na⁺, Li⁺, K⁺, Cs⁺, Rb⁺, substitutedand unsubstituted ammonium cations, and the like) with an aldehydederivative, such as unsubstituted alkyl aldehyde derivatives, includingformaldehyde, acetaldehyde, propylaldehyde, and the like, as well asmixtures thereof. Examples of such stabilizing agents include, but arenot limited to, commercial products such as Versa® 4, Versa® 7, Versa®77 (National Starch and Chemical Co.); Lomar® D (Diamond ShamrockChemical Co.); Daxad® 19, Daxad® K (W. R. Grace & Co.); Tamol® SN (Rohm& Haas); and the like. Other useful anionic stabilizing agents includepolymers or random copolymers of styrene and an acrylic acid salt,styrene and a methacrylic acid salt, styrene and a maleic acid salt,block copolymers comprising acrylates or methacrylates, and the like, aswell as mixtures thereof.

Nonionic pigment stabilizing agents (or dispersing agents ordispersants) or surfactants can also be used in inks for the presentinvention, such as ethoxylated monoalkyl or dialkyl phenols, includingIgepal® CA and CO series materials (Rhone-Poulenc Co., such as Igepal®CA-630, CO-630, and the like); Surfynol® series materials from AirProducts and Chemicals Co.; and Triton® series materials (Union CarbideCompany). These nonionic surfactants or dispersants can be used alone orin combination with anionic or cationic dispersants.

The ratio of pigment to stabilizing agent by weight typically is fromabout 1:0.01 to about 1:4, preferably from about 1:0.1 to about 1:2, andmore preferably from about 1:0.10 to about 1:1.5, although the ratio canbe outside of these ranges.

The ratio of naphthalene substituent to aldehyde in the aforementionedanionic stabilizing agents typically is about 1:1, although this ratiocan be different depending on the stoichiometry of the feed stock andreaction condition, and can readily be adjusted to obtain a dispersanthaving a desired molecular weight and the desired ratio of naphthalenesubstituent to aldehyde. The weight average molecular weight of thepigment stabilizing agent is generally less than about 50,000,preferably less than about 25,000, and more preferably less than about10,000, although the weight average molecular weight can be outside ofthese ranges. The pigment dispersion preferably contains enoughdispersant to stabilize the pigment particles in water, but not so muchas to affect adversely properties of the dispersion and ink such asviscosity, stability, and optical density.

Dye colorants are those colorants that are soluble in the aqueous liquidvehicle. The dye can be selected from the suitable colorants listed inthe Color Index, published jointly by American Association of TextileChemist and Colorists (AATCC) and The Society of Dyers and Colorists inBradford, England; BUYER'S GUIDE for Textile Chemist and Colorist,published by AATCC, and the like. Any suitable dye or mixture of dyesthat is compatible with the other ink ingredients can be used. Watersoluble or water dispersible anionic dyes, direct dyes, reactive dyes,and cationic dyes can be selected. Examples of suitable dyes include,but are not limited to, Food dyes such as Food Black No. 1, Food BlackNo. 2, Food Red No. 40, Food Blue No. 1, Food Yellow No. 7, and thelike; FD & C dyes; Acid Black dyes (No. 1, 7, 9, 24, 26, 48, 52, 58, 60,61, 63, 92, 107, 109, 118, 119, 131, 140, 155, 156, 172, 194, and thelike); Acid Red dyes (No. 1, 8, 32, 35, 37, 52, 57, 92, 115, 119, 154,249, 254, 256, and the like); Acid Blue dyes (No. 1, 7, 9, 25, 40, 45,62, 78, 80, 92, 102, 104, 113, 117, 127, 158, 175, 183, 193, 209, andthe like); Acid Yellow dyes (No. 3, 7, 17, 19, 23, 25, 29, 38, 42, 49,59, 61, 72, 73, 114, 128, 151, and the like); Direct Black dyes (No. 4,14, 17, 22, 27, 38, 51, 112, 117, 154, 168, and the like); Direct Bluedyes (No. 1, 6, 8, 14, 15, 25, 71, 76, 78, 80, 86, 90, 106, 108, 123,163, 165, 199, 226, and the like); Direct Red dyes (No. 1, 2, 16, 23,24, 28, 39, 62, 72, 236, 337, and the like); Direct Yellow dyes (No. 4,11, 12, 27, 28, 33, 34, 39, 50, 58, 86, 100, 106, 107, 118, 127, 132,142, 157, and the like); anthraquinone dyes; monoazo dyes; disazo dyes;phthalocyanine derivatives, including various phthalocyanine sulfonatesalts; aza (18) annulenes; Formazan copper complexes;triphenodioxazines; Bernacid Red 2BMN; Pontamine Brilliant Bond Blue A;Pontamine; Caro direct Turquoise FBL Supra Conc. (Direct Blue 199),available from Carolina Color and Chemical; Special Fast Turquoise 8GLLiquid (Direct Blue 86), available from Mobay Chemical; Intrabond LiquidTurquoise GLL (Direct Blue 86), available from Crompton and Knowles;Cibracron Brilliant Red 38-A (Reactive Red 4), available from AldrichChemical; Reactive Dyes (e.g. Reactive Black 5, Reactive Blue 2,Reactive Blue 4, Reactive Blue 15, Reactive Orange 16, Reactive Red 2,Reactive Red 4, Reactive Yellow 2, and Reactive Yellow 81) from AldrichChemical Co.; Reactive Red 180 and its hydrolyzed form from MitsubishiChemical Co. of Japan; Drimarene Brilliant Red X-2B (Reactive Red 56),available from Pylam, Inc.; Levafix Brilliant Red E-4B, available fromMobay Chemical; Levafix Brilliant Red E-6BA, available from MobayChemical; Procion Red H8B (Reactive Red 31), available from ICI ofAmerica (Zeneca Co.); Pylam Certified D&C Red #28 (Acid Red 92),available from Pylam; Direct Brilliant Pink B Ground Crude, availablefrom Crompton & Knowles; Cartasol Yellow GTF Presscake, available fromSandoz, Inc.; Tartrazine Extra Conc. (FD&C Yellow #5, Acid Yellow 23),available from Sandoz; Carodirect Yellow RL (Direct Yellow 86),available from Carolina Color and Chemical; Cartasol Yellow GTF LiquidSpecial 110, available from Sandoz, Inc.; D&C Yellow #10 (Acid Yellow3), available from Tricon; Yellow Shade 16948, available from Tricon;Basacid Black X34, available from BASF; Carta Black 2GT, available fromSandoz, Inc.; Neozapon Red 492, available from BASF; Orasol Red Gavailable from Ciba-Geigy; Direct Brilliant Pink B (Crompton-Knolls);Aizen Spilon Red C-BH (Hodogaya Chemical Company); Kayanol Red 3BL(Nippon Kayaku Company); Levanol Brilliant Red 3BW (Mobay ChemicalCompany); Levaderm Lemon Yellow (Mobay Chemical Company); Spirit FastYellow 3G; Aizen Spilon Yellow C-GNH (Hodogaya Chemical Company); SiriusSupra Yellow GD 167; Cartasol Brilliant Yellow 4GF (Sandoz); PergasolYellow CGP (Ciba-Geigy); Orasol Black RL (Ciba-Geigy); Orasol Black RLP(Ciba-Geigy); Savinyl Black RLS (Sandoz); Dermacarbon 2GT (Sandoz);Pyrazol Black BG (ICI); Morfast Black Conc A (Morton-Thiokol); DiazolBlack RN Quad (ICI); Orasol Blue GN (Ciba-Geigy); Savinyl Blue GLS(Sandoz); Luxol Blue MBSN (Morton-Thiokol); Sevron Blue 5GMF (ICI);Basacid Blue 750 (BASF); Bernacid Red, available from Berncolors,Poughkeepsie, N.Y.; Pontamine Brilliant Bond Blue; Berncolor Acid Yellow34; Telon Fast Yellow 4GL-175; BASF Basacid Black SE 0228; the Pro-Jet®series of dyes available from Zeneca Co., including Pro-Jet® Yellow I(Direct Yellow 86), Pro-Jet® Magenta I (Acid Red 249), Pro-Jet® Cyan I(Direct Blue 199), Pro-Jet® Black I (Direct Black 168), Pro-Jet® Yellow1-G (Direct Yellow 132), and Pro-Jet® waterfast dyes; Aminyl BrilliantRed F-B, available from Sumitomo Chemical Company (Japan); the Duasyn®line of “salt-free” dyes available from Hoechst/Celanese, such asDuasyn® Direct Black HEF-SF (Direct Black 168), Duasyn® Black RL-SF(Reactive Black 31), Duasyn® Direct Yellow 6G-SF VP216 (Direct Yellow157), Duasyn® Brilliant Yellow GL-SF VP220 (Reactive Yellow 37), Duasyn®Acid Yellow XX-SF LP413 (Acid Yellow 23), Duasyn® Brilliant Red F3B-SFVP218 (Reactive Red 180), Duasyn® Rhodamine B-SF VP353 (Acid Red 52),Duasyn® Direct Turquoise Blue FRL-SF VP368 (Direct Blue 199), andDuasyn® Acid Blue AE-SF VP344 (Acid Blue 9); Dispersed Dyes; variousReactive dyes, including Reactive Black dyes, Reactive Blue dyes,Reactive Red dyes, and Reactive Yellow dyes; and the like; as well asmixtures thereof.

A dye colorant is present in the ink in any effective amount to providedesired color and optical density. Typically, the dye is present in anamount from about 0.01 to about 15 percent by weight of the ink,preferably from about 0.1 to about 10 percent by weight of the ink, morepreferably from about 1 to about 8 percent by weight of the ink, andeven more preferably from about 1 to about 5 percent by weight of theink, although the amount can be outside of these ranges. A mixture ofdyes in any desired proportion can also be employed to obtain a specificshade or hue.

The ink compositions of the present invention also contain an ABCB′A′ orBACA′B′ block copolymer wherein the A and A′ blocks contain one or moreethylene oxide repeat monomer units, the B and B′ blocks contain one ormore propylene oxide repeat monomer units, and the C block contains oneor more repeat monomer units of a dialkylsiloxane, alkyl aryl siloxane,or diarylsiloxane. Optionally, the A or B block and the C block can beseparated by an optional spacer group S. Optionally, the C block and theB′ or A′ blocks can be separated by an optional spacer group S′.Accordingly, the block copolymers of the present invention can also berepresented as ABSCS′B′A′ or BASCS′A′B′ block copolymers, wherein S andS′ are optional spacer groups.

The ABSCS′B′A′ and BASCS′A′B′ block copolymers suitable for the inks ofthe present invention have a linear structure (linear polymer backbone),and are to be distinguished from grafted or branched dimethylsiloxanecopolymers.

A and A′ are each blocks comprising one or more repeat monomer units ofethylene oxide. The A and A′ blocks can be either the same as each otheror different from each other in terms of chain length. A and A′preferably each have from 1 to about 10,000 repeat ethylene oxide units,although the number of repeat ethylene oxide units can be outside ofthis range.

B and B′ are each blocks comprising one or more repeat monomer units ofpropylene oxide. The B and B′ blocks can be either the same as eachother or different from each other in terms of chain length. B and B′preferably each have from 1 to about 10,000 repeat propylene oxideunits, although the number of repeat propylene oxide units can beoutside of this range.

C is a block comprising one or more repeat monomer units of analkylsiloxane, a dialkylsiloxane, an alkyl aryl siloxane, adiarylsiloxane, or mixtures thereof. The alkyl or aryl groups on thealkylsiloxane, dialkylsiloxane, alkyl aryl siloxane, and/ordiarylsiloxane repeat monomer units typically have from 1 to about 20carbon atoms, although the number of carbon atoms can be outside of thisrange. Particularly preferred repeat monomers for the C block includedimethyl siloxane, methyl ethyl siloxane, diethyl siloxane, methylphenylsiloxane, diphenyl siloxane, and the like. C preferably is selected sothat the number of repeat alkylsiloxane, dialkylsiloxane, alkyl arylsiloxane, and/or diarylsiloxane units in the ABSCS′B′A′ or BASCS′A′B′block copolymer is from 1 to about 5,000, although the number of repeatsiloxane units can be outside of this range.

S is an optional spacer group between the A or B blocks and the C block,and S′ is an optional spacer group between the C block and the B or A′blocks. In an ABSCSB′A′ block copolymer, when S is absent, the B blockis directly bonded to the C block, and in a BASCS′A′B′ block copolymer,when S is absent, the A block is directly bonded to the C block. In anABSCS′B′A′ block copolymer, when S′ is absent, the B′ block is directlybonded to the C block, and in a BASCS′A′B′ block copolymer, when S′ isabsent, the A′ block is directly bonded to the C block. S and S′ each,independently of the other, can be (but are not limited to) alkylenegroups, alkylene oxide groups, alkylsilyl groups, dialkylsilyl groups,alkylarylsilyl groups, diarylsilyl groups, propylenylalkylsilyl groups,propylenyldialkylsilyl groups, propylenylalkylarylsilyl groups,propylenyidiarylsilyl groups, alkylsiloxy groups, dialkylsiloxy groups,alkylarylsiloxy groups, diarylsiloxy groups, propyleneoxyalkylsilylgroups, propylenylalkylsiloxy groups, propyleneoxydialkylsilyl groups,propylenyidialkylsiloxy groups, propyleneoxyalkylarylsilyl groups,propylenylalkylarylsiloxy groups, propyleneoxydiarylsilyl groups,propylenyldiarylsiloxy groups, heteroatoms, or mixtures thereof.Examples of suitable alkylene S and S′ groups include those with from 1to about 10 carbon atoms, such as those of the formula —(CH₂)_(t)—wherein t is an integer of from 1 to about 10, such as methylene(—CH₂—), ethylene (—CH₂CH₂—), propylene (—CH₂CH₂CH₂—), and the like.Examples of suitable alkylene oxide S and S′ groups include those withfrom 1 to about 10 carbon atoms, such as methylene oxide (—CH₂O— or—OCH₂—), ethylene oxide (—CH₂CH₂O— or —OCH₂CH₂—), propylene oxide(—CH₂CH₂CH₂O— or —OCH₂CH₂CH₂—), and the like. Examples of suitablealkylsilyl S and S′ groups, dialkylsilyl S and S′ groups, alkylarylsilylS and S′ groups, diarylsilyl S and S′ groups, propylenylalkylsilyl S andS′ groups, propylenyldialkylsilyl S and S′ groups,propylenylalkylarylsilyl S and S′ groups, and propylenyldiarylsilyl Sand S′ groups include those wherein the alkyl moieties have from 1 toabout 10 carbon atoms and the aryl moieties have from 6 to about 20carbon atoms, such as dimethylsilyl (—Si(CH₃)₂—), methylethylsilyl(—Si(CH₃)(C₂H₅)—), methylphenylsilyl (—Si(CH₃)(C₆H₅)—), diphenylsilyl(—Si(C₆H₅)₂—), dimethylpropylenylsilyl (—C₃H₆—Si(CH₃)₂— or—Si(CH₃)₂—C₃H₆—), and the like. Examples of suitable alkylsiloxy S andS′ groups, dialkylsiloxy S and S′ groups, alkylarylsiloxy S and S′groups, diarylsiloxy S and S′ groups, propyleneoxyalkylsilyl S and S′groups, propylenylalkylsiloxy S and S′ groups, propyleneoxydialkylsilylS and S′ groups, propylenyldialkylsiloxy S and S′ groups,propyleneoxyalkylarylsilyl S and S′ groups, propylenylalkylarylsiloxy Sand S′ groups, propyleneoxydiarylsilyl S and S′ groups, andpropylenyldiarylsiloxy S and S′ groups include those wherein the alkylmoieties have from 1 to about 10 carbon atoms and the aryl moieties havefrom 6 to about 20 carbon atoms, such as dimethylsiloxy (—Si(CH₃)₂O—),methylethylsiloxy (—Si(CH₃)(C₂H₅)O—), methylphenylsiloxy(—Si(CH₃)(C₆H₅)O—), diphenylsiloxy (—Si(C₆H₅)₂O—),dimethylpropylenylsiloxy (—C₃H₆—Si(CH₃)₂O— or —Si(CH₃)₂—C₃H₆O— or—OC₃H₆—Si(CH₃)₂— or —OSi(CH₃)₂—C₃H₆—), and the like. Examples ofsuitable S and S′ heteroatoms include oxygen, nitrogen, phosphorus,sulfur, silicon, and the like, as well as mixtures thereof. Two or moreof the aforementioned suitable S and S′ groups can also be combined toprovide a spacer group; for example, a single spacer group S or S′ cancomprise both an alkylene group and a dialkyl silyl group, such as—(CH₂)_(t)—Si(CH₃)₂— or —Si(CH₃)₂—(CH₂)_(t)— wherein t is an integer offrom 1 to about 10.

The terminal groups on the block copolymer are bonded to the A and A′blocks in an ABCB′A′ block copolymer and are bonded to the B and B′blocks in a BACA′B′ block copolymer, and typically are hydrogen atoms,hydroxyl groups, alkyl groups, hydroxyl-substituted alkyl groups, oralkoxy groups, wherein the alkyl, hydroxyl-substituted alkyl, and alkoxygroups typically have from 1 to about 20 carbon atoms, although thenumber of carbon atoms can be outside of this range, and although otherterminal groups can be selected. Preferably the terminal group isselected to avoid a peroxy linkage; accordingly, if the atom of theblock immediately connected to the terminal group is an oxygen atom,terminal groups such as hydroxy groups or alkoxy groups preferably arenot selected to avoid peroxy linkages.

Suitable block copolymers for the inks of the present invention (alsoshowing the optional spacer groups) include those of the generalformulae

wherein R and R′ each, independently of the other, are hydrogen atoms,hydroxyl groups, alkyl groups (including linear, branched, and cyclicalkyl groups), typically with from 1 to about 30 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges,hydroxyl-substituted alkyl groups (including linear, branched, andcyclic alkyl groups), typically with from 1 to about 30 carbon atoms,although the number of carbon atoms can be outside of these ranges, oralkoxy groups (including linear, branched, and cyclic alkoxy groups),typically with from 1 to about 30 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, R₁ and R₂ each,independently of the other, is a hydrogen atom, an alkyl group,typically with from 1 to about 10 carbon atoms, although the number ofcarbon atoms can be outside of this range, or an aryl group, typicallywith from 6 to about 20 carbon atoms, although the number of carbonatoms can be outside of this range, i, z, p, and l are each integersrepresenting the numbers of repeat alkylene oxide monomer units, whereini, z, p, and l are each, independently of the other, typically from 1 toabout 10,000, although the values of i, z, p, and l can be outside ofthis range, y is an integer representing the number of repeat siloxanemonomer units, being typically from 1 to about 5,000, although the valueof y can be outside of this range, and S and S′ are optional spacergroups.

Specific examples of block copolymers suitable for the inks of thepresent invention include those of Formula 1 (which have no spacergroups):

those of Formula 2 (which have no spacer groups):

those of Formula 3 (which have spacer groups):

and those of Formula 4 (which have spacer groups):

wherein R and R′ each, independently of the other, are hydrogen atoms,hydroxyl groups, alkyl groups (including linear, branched, and cyclicalkyl groups), typically with from 1 to about 30 carbon atoms, althoughthe number of carbon atoms can be outside of these ranges,hydroxyl-substituted alkyl groups (including linear, branched, andcyclic alkyl groups), typically with from 1 to about 30 carbon atoms,although the number of carbon atoms can be outside of these ranges, oralkoxy groups (including linear, branched, and cyclic alkoxy groups),typically with from 1 to about 30 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, R₁ and R² each,independently of the other, is a hydrogen atom, an alkyl group,typically with from 1 to about 10 carbon atoms, although the number ofcarbon atoms can be outside of this range, or an aryl group, typicallywith from 6 to about 20 carbon atoms, although the number of carbonatoms can be outside of this range, i, z, p, and l are each integersrepresenting the numbers of repeat alkylene oxide monomer units, whereini, z, p, and l are each, independently of the other, typically from 1 toabout 10,000, although the values of x, y, m, and n can be outside ofthis range, y is an integer representing the number of repeat siloxanemonomer units, being typically from 1 to about 5,000, although the valueof y can be outside of this range, and j and k are each integersrepresenting the number of repeat —(CH₂)— units, being typically of from0 to about 10, although the values of j and k can be outside of thisrange, wherein j+k≧1.

An example of a material of Formula 1 is that of Formula 1A, wherein Ris selected to be a hydroxyl group and R′ is selected to be a hydrogenatom, so that the block copolymer has two terminal hydroxyl groups(which can also be described as terminal hydroxypropoxylate groups):

wherein i, z, y, p, l, R₁, and R₂ are as defined hereinabove for blockcopolymers of Formula 1. An example of a material of Formula 1A is thatwherein R₁ and R₂ are each selected to be methyl and i and l are eachselected to be 1, a material of Formula 1A(1):

wherein z, y, and p are as defined hereinabove for block copolymers ofFormula 1. This material, which can be called poly(dimethylsiloxane),ethoxylated, hydroxypropoxylate end-capped, is available from AldrichChemical Co., Milwaukee, Wis. as Catalog No. 48,271-4, ChemicalAbstracts Service Registry No. 68037-63-8.

An example of a material of Formula 2 is that of Formula 2A, wherein Ris selected to be a hydroxyl group and R′ is selected to be a hydrogenatom, so that the block copolymer has two terminal hydroxyl groups(which can also be described as terminal hydroxyethoxylate groups):

wherein z, i, y, l, p, R₁, and R₂ are as defined hereinabove forpolymers of Formula 2. An example of a material of Formula 2A is thatwherein R₁ and R₂ are each selected to be methyl and z and p are eachselected to be 1, a material of Formula 2A(1):

wherein i, y, and l are as defined hereinabove for polymers of Formula2. This material can be called poly(dimethylsiloxane), propoxylated,hydroxyethoxylate end-capped.

An example of a material of Formula 3 is that of Formula 3A, wherein Ris selected to be a hydroxyl group and R′ is selected to be a hydrogenatom, so that the block copolymer has two terminal hydroxyl groups(which can also be described as terminal hydroxypropoxylate groups):

wherein i, z, j, y, k, p, l, R₁, and R₂ are as defined hereinabove forpolymers of Formula 3. An example of a material of Formula 3A is thatwherein R₁ and R₂ are each selected to be methyl, j and k are eachselected to be 3, and i and l are each selected to be 1, a material ofFormula 3A(1):

wherein z, y, and p are as defined hereinabove for polymers of Formula3. This material can be called poly(dimethylsiloxane), propyleneethoxylated, hydroxypropoxylate end-capped.

An example of a material of Formula 4 is that of Formula 4A, wherein Ris selected to be a hydroxyl group and R′ is selected to be a hydrogenatom, so that the block copolymer has two terminal hydroxyl groups(which can also be described as terminal hydroxyethoxylate groups):

wherein z, i, j, y, k, l, p, R₁, and R₂ are as defined hereinabove forblock copolymers of Formula 4. An example of a material of Formula 4A isthat wherein R₁ and R₂ are each selected to be methyl, j and k are eachselected to be 3, and z and p are each selected to be 1, a material ofFormula 4A(1):

wherein i, y, and l are as defined hereinabove for block copolymers ofFormula 4. This material can be called poly(dimethylsiloxane), propylenepropoxylated, hydroxyethoxylate end-capped.

For illustration purposes, further examples of suitable ABSCS′B′A′ andBASCS′A′B′ block copolymers for the inks of the present invention willnow be presented. Type A block copolymers (those of Formula I andFormula II) have a C block with one or more alkylsiloxane ordialkylsiloxane repeat monomer units, wherein the alkyl groups of thealkylsiloxane or dialkylsiloxane each, independently of the other, havefrom 1 to about 10 carbon atoms. Type A materials include, but are notlimited to, the following:

wherein R and R′ each, independently of the other, can be hydrogenatoms, hydroxyl groups, alkyl groups (including linear, branched, andcyclic alkyl groups), typically with from 1 to about 30 carbon atoms,although the number of carbon atoms can be outside of these ranges,hydroxyl-substituted alkyl groups (including linear, branched, andcyclic alkyl groups), typically with from 1 to about 30 carbon atoms,although the number of carbon atoms can be outside of these ranges, oralkoxy groups (including linear, branched, and cyclic alkoxy groups),typically with from 1 to about 30 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, R₁ and R₂ each,independently of the other, are hydrogen atoms or alkyl groups(including linear, branched, and cyclic alkyl groups) typically withfrom 1 to about 10 carbon atoms, although the number of carbon atoms canbe outside of this range, either (a) R₃ and R₄ are ethylene oxide groupsand R₅ and R₆ are propylene oxide groups or (b) R₃ and R₄ are propyleneoxide groups and R₅ and R₆ are ethylene oxide groups, v, g, h, and u areeach, independently of the others, integers representing the number ofrepeat alkylene oxide groups, and typically are from 1 to about 10,000,and y is an integer representing the number of alkylsiloxane ordialkylsiloxane repeat groups, and typically is from 1 to about 5,000.In the block copolymers of Formula I, one spacer group is an alkylsiloxyor dialkylsiloxy group and one spacer group is an alkylsilyl ordialkylsilyl group. The following types of linkages between the spacergroups and the alkylene oxide groups are possible:

(wherein n is 2 in the case of ethylene oxide groups and 3 in the caseof propylene oxide groups).

For example, when R₁ and R₂ are selected as methyl groups, R₃ and R₄ areselected as propylene oxide groups, and R₅ and R₆ are selected asethylene oxide groups, the block copolymer can be of Formula IA:

R—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(C₂H₄O)_(h)—(C₃H₆O)_(u)—R′  IA

When R and R′ are both hydrogen atoms, the material is of the formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)₂O—(Si (CH₃)₂O)_(y—)Si(CH₃)₂—(C₂H₄O)_(h)—(C₃H₆O)_(u)—H

which has two terminal hydroxyl groups. When R and R′ are both methylgroups, the material is of the formula

H₃C—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(C₂H₄O)_(h)—(C₃H₆O)_(u)—CH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methyl group, the material is of the formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(C₂H₄O)_(h)—(C₃H₆O)_(u)—CH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R₁ and R₂ are selected as methyl groups, R₃ and R₄ are selected aspropylene oxide groups, and R₅ and R₆ are selected as ethylene oxidegroups, the block copolymer can also be of Formula IA′:

R—(C₃H₆O)_(v)—(C₂H₄O)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₂H₄)_(h)—(OC₃H₆)_(u)—R′  IA′

When R and R′ are both hydroxyl groups, the material is of the formula

HO—(C₃H₆O)_(v)—(C₂H₄O)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OH

which has two terminal hydroxyl groups. When R and R′ are both methoxygroups, the material is of the formula

H₃C—(C₃H₆O)_(v)—(C₂H₄O)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₂H₄)_(h)—(OC₃H₆)_(u)—CH₃

which has two terminal methoxy groups. When R is a hydroxyl group and R′is a methoxy group, the material is of the formula

 HO—(C₃H₆O)_(v)—(C₂H₄O)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.

When R₁ and R₂ are selected as methyl groups, R₃ and R₄ are selected aspropylene oxide groups, and R₅ and R₆ are selected as ethylene oxidegroups, the block copolymer can also be of Formula IB:

R—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₂H₄)_(h)—(OC₃H₆)_(u)—R′  IB

When R is a hydrogen atom and R′ is a hydroxyl group, the material is ofthe formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OH

which has two terminal hydroxyl groups. When R is a methyl group and R′is a methoxy group, the material is of the formula

H₃C—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methoxy group, the material is of the formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R is a methyl group and R′ is a hydroxyl group, the material is ofthe formula

H₃C—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OH

which has one terminal hydroxyl group and one terminal methoxy group.

When R₁ and R₂ are selected as methyl groups, R₃ and R₄ are selected asethylene oxide groups, and R₅ and R₆ are selected as propylene oxidegroups, the block copolymer can be of Formula IC:

R—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(C₃H₆O)_(h)—(C₂H₄O)_(u)—R′  IC

When R and R′ are both hydrogen atoms, the material is of the formula

 H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(C₃H₆O)_(h)—(C₂H₄O)_(u)—H

which has two terminal hydroxyl groups. When R and R′ are both methylgroups, the material is of the formula

H₃C—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(C₃H₆O)_(h)—(C₂H₄O)_(u)—CH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methyl group, the material is of the formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(C₃H₆O)_(h)—(C₂H₄O)_(u)—CH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R₁ and R₂ are selected as methyl groups, R₃ and R₄ are selected asethylene oxide groups, and R₅ and R₆ are selected as propylene oxidegroups, the block copolymer can also be of Formula IC′:

R—(C₂H₄O)_(v)—(C₃H₆O)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₃H₆)_(h)—(OC₂H₄)_(u)—R′  IC′

When R and R′ are both hydroxyl groups, the material is of the formula

HO—(C₂H₄O)_(v)—(C₃H₆O)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OH

which has two terminal hydroxyl groups. When R and R′ are both methoxygroups, the material is of the formula

H₃CO—(C₂H₄O)_(v)—(C₃H₆O)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has two terminal methoxy groups. When R is a hydroxyl group and R′is a methoxy group, the material is of the formula

HO—(C₂H₄O)_(v)—(C₃H₆O)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.

When R₁ and R₂ are selected as methyl groups, R₃ and R₄ are selected asethylene oxide groups, and R₅ and R₆ are selected as propylene oxidegroups, the block copolymer can also be of Formula ID:

 R—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₃H₆)_(h)—(OC₂H₄)_(u)—R′  ID

When R is a hydrogen atom and R′ is a hydroxyl group, the material is ofthe formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OH

which has two terminal hydroxyl groups. When R is a methyl group and R′is a methoxy group, the material is of the formula

H₃C—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methoxy group, the material is of the formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R is a methyl group and R′ is a hydroxyl group, the material is ofthe formula

H₃C—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OH

which has one terminal hydroxyl group and one terminal methoxy group.

Type A materials also include, but are not limited to, the following:

wherein R and R′ each, independently of the other, can be hydrogenatoms, hydroxyl groups, alkyl groups (including linear, branched, andcyclic alkyl groups), typically with from 1 to about 30 carbon atoms,although the number of carbon atoms can be outside of these ranges,hydroxyl-substituted alkyl groups (including linear, branched, andcyclic alkyl groups), typically with from 1 to about 30 carbon atoms,although the number of carbon atoms can be outside of these ranges, oralkoxy groups (including linear, branched, and cyclic alkoxy groups),typically with from 1 to about 30 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, R₁ and R₂ each,independently of the other, are hydrogen atoms or alkyl groups(including linear, branched, and cyclic alkyl groups) typically withfrom 1 to about 10 carbon atoms, although the number of carbon atoms canbe outside of this range, either (a) R₃ and R₄ are ethylene oxide groupsand R₅ and R₆ are propylene oxide groups or (b) R₃ and R₄ are propyleneoxide groups and R₅ and R₆ are ethylene oxide groups, v, g, h, and u areeach, independently of the others, integers representing the number ofrepeat alkylene oxide groups, and typically are from 1 to about 10,000,y is an integer representing the number of alkylsiloxane ordialkylsiloxane repeat groups, and typically is from 1 to about 5,000,and a and b each, independently of the other, are integers of from 0 toabout 10, wherein the sum of a+b≧1. In the block copolymers of FormulaII, one spacer group is a combination of an alkylene group and analkylsiloxy or dialkylsiloxy group and one spacer group is a combinationof an alkylene group and an alkylsilyl or dialkylsilyl group. Thefollowing types of linkages between the spacer groups and the alkyleneoxide groups are possible:

(wherein n is 2 in the case of ethylene oxide groups and 3 in the caseof propylene oxide groups).

For example, when R₁ and R₂ are selected as methyl groups, R₃ and R₄ areselected as propylene oxide groups, and R₅ and R₆ are selected asethylene oxide groups, the block copolymer can be of Formula IIA:

R—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH2)_(b)—(C₂H₄O)_(h)—(C₃H₆O)_(u)—R′  IIA

When R and R′ are both hydrogen atoms, the material is of the formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(C₂H₄O)_(h)—(C₃H₆O)_(u)—H

which has two terminal hydroxyl groups. When R and R′ are both methylgroups, the material is of the formula

H₃C—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(C₂H₄O)_(h)—(C₃H₆O)_(u)—CH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methyl group, the material is of the formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(C₂H₄O)_(h)—(C₃H₆O)_(u)—CH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R₁ and R₂ are selected as methyl groups, R₃ and R₄ are selected aspropylene oxide groups, and R₅ and R₆ are selected as ethylene oxidegroups, the block copolymer can also be of Formula IIA′:

R—(C₃H₆O)_(v)—(C₂H₄O)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—R′  IIA′

When R and R′ are both hydroxyl groups, the material is of the formula

HO—(C₃H₆O)_(v)—(C₂H₄O)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OH

which has two terminal hydroxyl groups. When R and R′ are both methoxygroups, the material is of the formula

H₃C—(C₃H₆O)_(v)—(C₂H₄O)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—CH₃

which has two terminal methoxy groups. When R is a hydroxyl group and R′is a methoxy group, the material is of the formula

HO—(C₃H₆O)_(v)—(C₂H₄O)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.

When R₁ and R₂ are selected as methyl groups, R₃ and R₄ are selected aspropylene oxide groups, and R₅ and R₆ are selected as ethylene oxidegroups, the block copolymer can also be of Formula IIB:

R—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—R′  IIB

When R is a hydrogen atom and R′ is a hydroxyl group, the material is ofthe formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OH

which has two terminal hydroxyl groups. When R is a methyl group and R′is a methoxy group, the material is of the formula

H₃C—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—CH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methoxy group, the material is of the formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R is a methyl group and R′ is a hydroxyl group, the material is ofthe formula

H₃C—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OH

which has one terminal hydroxyl group and one terminal methoxy group.

When R₁ and R₂ are selected as methyl groups, R₃ and R₄ are selected asethylene oxide groups, and R₅ and R₆ are selected as propylene oxidegroups, the block copolymer can be of Formula IIC:

R—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(C₃H₆O)_(h)—(C₂H₄O)_(u)—R′  IIC

When R and R′ are both hydrogen atoms, the material is of the formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(C₃H₆O)_(h)—(C₂H₄O)_(u)—H

which has two terminal hydroxyl groups. When R and R′ are both methylgroups, the material is of the formula

H₃C—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(C₃H₆O)_(h)—(C₂H₄O)_(u)—CH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methyl group, the material is of the formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(C₃H₆O)_(h)—(C₂H₄O)_(u)—CH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R₁ and R₂ are selected as methyl groups, R₃ and R₄ are selected asethylene oxide groups, and R₅ and R₆ are selected as propylene oxidegroups, the block copolymer can also be of Formula IIC′:

R—(C₂H₄O)_(v)—(C₃H₆O)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—R′  IIC′

When R and R′ are both hydroxyl groups, the material is of the formula

HO—(C₂H₄O)_(v)—(C₃H₆O)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OH

which has two terminal hydroxyl groups. When R and R′ are both methoxygroups, the material is of the formula

H₃CO—(C₂H₄O)_(v)—(C₃H₆O)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has two terminal methoxy groups. When R is a hydroxyl group and R′is a methoxy group, the material is of the formula

HO—(C₂H₄O)_(v)—(C₃H₆O)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.

When R₁ and R₂ are selected as methyl groups, R₃ and R₄ are selected asethylene oxide groups, and R₅ and R₆ are selected as propylene oxidegroups, the block copolymer can also be of Formula IID:

R—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—R′  IID

When R is a hydrogen atom and R′ is a hydroxyl group, the material is ofthe formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OH

which has two terminal hydroxyl groups. When R is a methyl group and R′is a methoxy group, the material is of the formula

H₃C—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—CH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methoxy group, the material is of the formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R is a methyl group and R′ is a hydroxyl group, the material is ofthe formula

H₃C—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OH

which has one terminal hydroxyl group and one terminal methoxy group.

Type B block copolymers (those of Formula III and Formula IV) have a Cblock with one or more alkylarylsiloxane repeat monomer units, whereinthe alkyl group of the alkylarylsiloxane has from 1 to about 10 carbonatoms and the aryl group of the alkylarylsiloxane has from 6 to about 20carbon atoms. Type B materials include, but are not limited to, thefollowing:

wherein R and R′ each, independently of the other, can be hydrogenatoms, hydroxyl groups, alkyl groups (including linear, branched, andcyclic alkyl groups), typically with from 1 to about 20 carbon atoms,although the number of carbon atoms can be outside of these ranges,hydroxyl-substituted alkyl groups (including linear, branched, andcyclic alkyl groups), typically with from 1 to about 30 carbon atoms,although the number of carbon atoms can be outside of these ranges, oralkoxy groups (including linear, branched, and cyclic alkoxy groups),typically with from 1 to about 30 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, R₇ is an alkyl group(including linear, branched, and cyclic alkyl groups) typically withfrom 1 to about 10 carbon atoms, although the number of carbon atoms canbe outside of this range, R₈ is an aryl group, typically with from 6 toabout 20 carbon atoms, although the number of carbon atoms can beoutside of this range, either (a) R₃ and R₄ are ethylene oxide groupsand R₅ and R₆ are propylene oxide groups or (b) R₃ and R₄ are propyleneoxide groups and R₅ and R₆ are ethylene oxide groups, v, g, h, and u areeach, independently of the others, integers representing the number ofrepeat alkylene oxide groups, and typically are from 1 to about 10,000,and y is an integer representing the number of alkylarylsiloxane repeatgroups, and typically is from 1 to about 5,000. In the block copolymersof Formula III, one spacer group is an alkylarylsiloxy group and onespacer group is an alkylarylsilyl group. The following types of linkagesbetween the spacer groups and the alkylene oxide groups are possible:

(wherein n is 2 in the case of ethylene oxide groups and 3 in the caseof propylene oxide groups).

For example, when R₇ is selected as a methyl group and R₈ is selected asa phenyl group (φ), R₃ and R₄ are selected as propylene oxide groups,and R₅ and R₆ are selected as ethylene oxide groups, the block copolymercan be of Formula IIIA:

R—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(C₂H₄O)_(h)—(C₃H₆O)_(u)—R′  IIIA

When R and R′ are both hydrogen atoms, the material is of the formula

 H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(C₂H₄O)_(h)—)C₃H₆O)_(u)—H

which has two terminal hydroxyl groups. When R and R′ are both methylgroups, the material is of the formula

H₃C—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(C₂H₄O)_(h)—(C₃H₆O)_(u)—CH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methyl group, the material is of the formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(C₂H₄O)_(h)—(C₃H₆O)_(u)—CH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R₇ is selected as a methyl group and R₈ is selected as a phenylgroup, R₃ and R₄ are selected as propylene oxide groups, and R₅ and R₆are selected as ethylene oxide groups, the block copolymer can also beof Formula IIIA′:

R—(C₃H₆O)_(v)—(C₂H₄O)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—R′  IIIA′

When R and R′ are both hydroxyl groups, the material is of the formula

HO—(C₃H₆O)_(v)—(C₂H₄O)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OH

which has two terminal hydroxyl groups. When R and R′ are both methoxygroups, the material is of the formula

H₃CO—(C₃H₆O)_(v)—(C₂H₄O)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has two terminal methoxy groups. When R is a hydroxyl group and R′is a methoxy group, the material is of the formula

HO—(C₃H₆O)_(v)—(C₂H₄O)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.

When R₇ is selected as a methyl group and R₂ is selected as a phenylgroup, R₃ and R₄ are selected as propylene oxide groups, and R₅ and R₆are selected as ethylene oxide groups, the block copolymer can also beof Formula IIIB:

R—(OC₃H₆)_(v—(OC)₂H₄)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—R′

When R is a hydrogen atom and R′ is a hydroxyl group, the material is ofthe formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OH

which has two terminal hydroxyl groups. When R is a methyl group and R′is a methoxy group, the material is of the formula

H₃C—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methoxy group, the material is of the formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R is a methyl group and R′ is a hydroxyl group, the material is ofthe formula

H₃C—(OC₃H₆)_(v)—(OC₂H₄)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OH

which has one terminal hydroxyl group and one terminal methoxy group.

When R₇ is selected as a methyl group and R₈ is selected as a phenylgroup, R₃ and R₄ are selected as ethylene oxide groups, and R₅ and R₆are selected as propylene oxide groups, the block copolymer can be ofFormula IIIC:

R—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(C₃H₆O)_(h)—(C₂H₄O)_(u)—R′  IIIC

When R and R′ are both hydrogen atoms, the material is of the formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(C₃H6O)_(h)—(C₂H₄O)_(u)—H

which has two terminal hydroxyl groups. When R and R′ are both methylgroups, the material is of the formula

H₃C—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(C₃H₆O)_(h)—(C₂H₄O)_(u)—CH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methyl group, the material is of the formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(C₃H₆O)_(h)—(C₂H₄O)_(u)—CH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R₇ is selected as a methyl group and R₈ is selected as a phenylgroup, R₃ and R₄ are selected as ethylene oxide groups, and R₅ and R₆are selected as propylene oxide groups, the block copolymer can also beof Formula IIIC′:

R—(C₂H₄O)_(v)—(C₃H₆O)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—R′  IIIC′

When R and R′ are both hydroxyl groups, the material is of the formula

HO—(C₂H₄O)_(v)—(C₃H₆O)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₃H₆)_(h)(OC₂H₄)_(u)—OH

which has two terminal hydroxyl groups. When R and R′ are both methoxygroups, the material is of the formula

H₃CO—(C₂H₄O)_(v)—(C₃H₆O)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has two terminal methoxy groups. When R is a hydroxyl group and R′is a methoxy group, the material is of the formula

HO—(C₂H₄O)_(v)—(C₃H₆O)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.

When R₇ is selected as a methyl group and R₈ is selected as a phenylgroup, R₃ and R₄ are selected as ethylene oxide groups, and R₅ and R₆are selected as propylene oxide groups, the block copolymer can also beof Formula IIID:

R—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—R′  IIID

When R is a hydrogen atom and R′ is a hydroxyl group, the material is ofthe formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OH

which has two terminal hydroxyl groups. When R is a methyl group and R′is a methoxy group, the material is of the formula

H₃C—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methoxy group, the material is of the formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)Si(CH₃)(φ)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R is a methyl group and R′ is a hydroxyl group, the material is ofthe formula

H₃C—(OC₂H₄)_(v)—(OC₃H₆)_(g)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OH

which has one terminal hydroxyl group and one terminal methoxy group.

Type B materials also include, but are not limited to, the following:

wherein R and R′ each, independently of the other, can be hydrogenatoms, hydroxyl groups, alkyl groups (including linear, branched, andcyclic alkyl groups), typically with from 1 to about 20 carbon atoms,although the number of carbon atoms can be outside of these ranges,hydroxyl-substituted alkyl groups (including linear, branched, andcyclic alkyl groups), typically with from 1 to about 30 carbon atoms,although the number of carbon atoms can be outside of these ranges, oralkoxy groups (including linear, branched, and cyclic alkoxy groups),typically with from 1 to about 30 carbon atoms, although the number ofcarbon atoms can be outside of these ranges, R₇ is an alkyl group(including linear, branched, and cyclic alkyl groups) typically withfrom 1 to about 10 carbon atoms, although the number of carbon atoms canbe outside of this range, R₈ is an aryl group, typically with from 6 toabout 20 carbon atoms, although the number of carbon atoms can beoutside of this range, either (a) R₃ and R₄ are ethylene oxide groupsand R₅ and R₆ are propylene oxide groups or (b) R₃ and R₄ are propyleneoxide groups and R₅ and R₆ are ethylene oxide groups, v, g, h, and u areeach, independently of the others, integers representing the number ofrepeat alkylene oxide groups, and typically are from 1 to about 10,000,y is an integer representing the number of dialkylsiloxane repeatgroups, and typically is from 1 to about 5,000, and a and b each,independently of the other, are integers of from 0 to about 10, whereinthe sum of a+b≧1. In the polymers of Formula IV, one spacer group is acombination of an alkylene group and an alkylarylsiloxy group and onespacer group is a combination of an alkylene group and an alkylarylsilylgroup. The following types of linkages between the spacer groups and thealkylene oxide groups are possible:

(wherein n is 2 in the case of ethylene oxide groups and 3 in the caseof propylene oxide groups).

For example, when R₇ is selected as a methyl group and R₈ is selected asa phenyl group, R₃ and R₄ are selected as propylene oxide groups, and R₅and R₆ are selected as ethylene oxide groups, the block copolymer can beof Formula IVA:

R—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)

(φ)—(CH₂)_(b)—(C₂H₄O)_(h)—(C₃H₆O)_(u)—R′  IVA

When R and R′ are both hydrogen atoms, the material is of the formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)

(φ)—(CH₂)_(b)—(C₂H₄O)_(h)—(C₃H₆

O)_(u)—H

which has two terminal hydroxyl groups. When R and R′ are both methylgroups, the material is of the formula

H₃C—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(C₂H₄O)_(h)—(C₃H₆O)_(u)—CH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methyl group, the material is of the formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)

—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)

(φ)—(CH₂)_(b)—(C₂H₄O)_(h)—(C₃H₆

O)_(u)—CH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R₇ is selected as a methyl group and R₈ selected as a phenyl group,R₃ and R₄ are selected as propylene oxide groups, and R₅ and R₆ areselected as ethylene oxide groups, the block copolymer can also be ofFormula IVA′:

R—(C₃H₆O)_(v)—(C₂H₄O)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)

(φ)—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)

_(u)—R′  IVA′

When R and R′ are both hydroxyl groups, the material is of the formula

HO—(C₃H₆O)_(v)—(C₂H₄O)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)

(φ)—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)

_(u)—OH

which has two terminal hydroxyl groups. When R and R′ are both methoxygroups, the material is of the formula

 H₃CO—(C₃H₆O)_(v)—(C₂H₄O)_(g)—(CH₂)_(a)

—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)

_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has two terminal methoxy groups. When R is a hydroxyl group and R′is a methoxy group, the material is of the formula

HO—(C₃H₆O)_(v)—(C₂H₄O)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)Si(CH₃)(φ)—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.

When R₇ is selected as a methyl group and R₈ is selected as a phenylgroup, R₃ and R₄ are selected as propylene oxide groups, and R₅ and R₆are selected as ethylene oxide groups, the block copolymer can also beof Formula IVB:

R—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—R′  IVB

When R is a hydrogen atom and R′ is a hydroxyl group, the material is ofthe formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OH

which has two terminal hydroxyl groups. When R is a methyl group and R′is a methoxy group, the material is of the formula

H₃C—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)

_(b)—(OC₂H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methoxy group, the material is of the formula

H—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)

(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(OC₂

H₄)_(h)—(OC₃H₆)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R is a methyl group and R′ is a hydroxyl group, the material is ofthe formula

H₃C—(OC₃H₆)_(v)—(OC₂H₄)_(g)—(CH₂)_(a)—Si(CH₃)

(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(OC₂H₄)

_(h)—(OC₃H₆)_(u)—OH

which has one terminal hydroxyl group and one terminal methoxy group.

When R₇ is selected as a methyl group and R₈ is selected as a phenylgroup, R₃ and R₄ are selected as ethylene oxide groups, and R₅ and R₆are selected as propylene oxide groups, the block copolymer can be ofFormula IVC:

R—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)

(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(C₃

H₆O)_(h)—(C₂H₄O)_(u)—R′  IVC

When R and R′ are both hydrogen atoms, the material is of the formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)

(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(C₃

H₆O)_(h)—(C₂H₄O)_(u)—H

which has two terminal hydroxyl groups. When R and R′ are both methylgroups, the material is of the formula

H₃C—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)

(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(C₃

H₆O)_(h)—(C₂H₄O)_(u)—CH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methyl group, the material is of the formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)

(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)

(φ)—(CH₂)_(b)—(C₃

H₆O)_(h)—(C₂H₄O)_(u)—CH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R₇ is selected as a methyl group and R₈ is selected as a phenylgroup, R₃ and R₄ are selected as ethylene oxide groups, and R₅ and R₆are selected as propylene oxide groups, the block copolymer can also beof Formula IVC′:

R—(C₂H₄O)_(v)—(C₃H₆O)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—R′  IVC′

When R and R′ are both hydroxyl groups, the material is of the formula

HO—(C₂H₄O)_(v)—(C₃H₆O)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OH

which has two terminal hydroxyl groups. When R and R′ are both methoxygroups, the material is of the formula

H₃CO—(C₂H₄O)_(v)—(C₃H₆O)_(g)—(CH₂)_(a)Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has two terminal methoxy groups. When R is a hydroxyl group and R′is a methoxy group, the material is of the formula

HO—(C₂H₄O)_(v)—(C₃H₆O)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.

When R₇ is selected as a methyl group and R₈ is selected as a phenylgroup, R₃ and R₄ are selected as ethylene oxide groups, and R₅ and R₆are selected as propylene oxide groups, the block copolymer can also beof Formula IVD:

R—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)Si(CH₃)(φ)—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—R′  IVD

When R is a hydrogen atom and R′ is a hydroxyl group, the material is ofthe formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OH

which has two terminal hydroxyl groups. When R is a methyl group and R′is a methoxy group, the material is of the formula

H₃C—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has two terminal methoxy groups. When R is a hydrogen atom and R′is a methoxy group, the material is of the formula

H—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)—Si(CH₃)(φ)—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OCH₃

which has one terminal hydroxyl group and one terminal methoxy group.When R is a methyl group and R′ is a hydroxyl group, the material is ofthe formula

H₃C—(OC₂H₄)_(v)—(OC₃H₆)_(g)—(CH₂)_(a)—Si(CH₃)(φ)O—(Si(CH₃)(φ)O)_(y)Si(CH₃)(φ)—(CH₂)_(b)—(OC₃H₆)_(h)—(OC₂H₄)_(u)—OH

which has one terminal hydroxyl group and one terminal methoxy group.

ABCBA and BACAB copolymers suitable for the inks of the presentinvention can be obtained commercially from, for example, AldrichChemical Co., Milwaukee, Wis.

In addition, alkylene oxide/siloxane copolymers suitable for the inks ofthe present invention can be obtained by the reaction of a hydrideterminated polydialkyl siloxane (for example, polydimethylsiloxane,H—Si(CH₃)₂—O—(Si(CH₃)₂—O)y—Si(CH₃)₂H) with polyols (—OH containinggroups) containing polyethyleneoxide units, polypropyleneoxide units, ora mixture thereof in the presence of metal catalyst (for example, zincchlorides, zinc acetates, zinc octoates, iron chlorides, iron acetates,iron octoates, tin chlorides, tin acetates, tin octoates, platinumcomplexes, dibutyl tin dilaurate, tributyl tin oxide, dibutylacetoxytin, Pd/C, or the like).

Further, alkylene oxide/siloxane copolymers suitable for the inks of thepresent invention can be obtained by the reaction of a hydrideterminated polydialkyl siloxane (for example, polydimethylsiloxane,H—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂H) with vinyl or allyl ethers ofpolyols (containing one —OH group or one ether group), including thosematerials containing polyethyleneoxide units, polypropyleneoxide units,or a mixture thereof in the presence of a metal catalyst (for example,zinc chlorides, zinc acetates, zinc octoates, iron chlorides, ironacetates, iron octoates, tin chlorides, tin acetates, tin octoates,platinum complexes, dibutyl tin dilaurate, tributyl tin oxide, dibutylacetoxytin, Pd/C, or the like).

Exemplary reactions (each taking place in the presence of one or moremetal catalysts) are as follows:

H—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂H+HO—(C₃H₆O)_(e)—(C₂H₄O)_(f)—R→RO—(C₂H₄O)_(f)—(C₃H₆O)_(e)—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂—(C₃H₆O)_(e)—(C₂H₄O)_(f)—R+2H₂H—Si(CH₃)₂—O(Si(CH₃)₂—O)O—O)_(y)—Si(CH₃)₂—(C₂H₄O)_(f)—(C₃H₆O)_(e)—R′+2H_(2H—Si(CH)₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂H+HO—(C₃H₆O)_(e)—(C₂H₄O)_(f)—R→RO—(C₂H₄O)_(f)—(C₃H₆O)_(e)—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂—(C₃H₆O)_(e—Si(CH)₃)₂H+HO—(C₂H₄O)_(f)—(C₃H₆O)_(e)—R→RO—(C₃H₆O)_(e)—(C₂H₄O)_(f)—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂—(C₂H₄O)_(f)—(C₃H₆O)_(e)—R+2H₂4H—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂H+4HO—(C₃H₆O)_(e)—(C₂H₄O)_(f)—R+4HO—(C₃H₆O)_(f)—(C₂H₄O)_(e)—R′→RO—(C₂H₄O)_(f)—(C₃H₆O)_(e)—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂—(C₃H₆O)_(e)—(C₂H₄O)_(f)—R+R′O—(C₃H₆O)_(e)—(C₂H₄O)_(f)—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂—(C₃H₆O)_(e)—(C₂H₄O)_(f)—R′+R′O—(C₃H4HO—(C₃H₆O)_(e)—(C₂H₄O)_(f)—R′+4HO—(C₂H₄O)_(e)—R→RO—(C₃H₆O)_(e)—(C₂H₄O)_(f)—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂—(C₂H₄O)_(f)—(C₃H₆O)_(e)—R+R′O—(C

wherein R, R′ and y are as defined hereinabove with respect to Formulae1, 2, 3, and 4, and e=i=l and f=z=p wherein i, l, z, and p are asdefined hereinabove with respect to Formulae 1, 2, 3, and 4.

The following reactions (either with or without metal catalysts) canalso be used to prepare block copolymers for inks of the presentinvention:

≡SiOH+HO(C₂H₄O)_(f)H→≡Si—O—(C₂H₄O)_(f)H

≡SiOH+HO(C₃H₆O)_(g)H→≡Si—O—(C₃H₆O)_(g)H

≡SiH+HO(C₂H₄O)_(f)H→≡Si—(C₂H₄O)_(f)H

≡SiH+HO(C₃H₆O)_(g)H→≡Si—(C₃H₆O)_(g)H

≡SiH+CH₂═CH₂—CH₂—(OC₂H₄O)_(f)

H(+catalyst)→≡Si—(CH₂)₃—(OC₂H₄)_(f)OH

≡SiH+CH₂═CH₂—CH₂—(OC₃H₆O)_(g)

H(+catalyst)→≡Si—(CH₂)₃—(OC₃H₆)_(g)OH

wherein f and g are each independently integers of from 1 to about15,000.

Alkylene oxide/siloxane copolymers suitable for the inks of the presentinvention can also be obtained by the reaction of a polydimethylsiloxanecomprising two active terminal ≡SiH groups(H—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂H) with corresponding vinyl or allygroup containing polyethyleneoxide, polypropyleneoxide, or a mixturethereof in the presence of a metal catalyst.

Alkylene oxide/siloxane block copolymers suitable for the inks of thepresent invention can also be obtained by the following reactions withvinyl or allyl compounds in the presence of a metal catalyst:

H—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂H+2CH₂═CH—(CH₂)_(r-2)—(C₂H₄O)_(f)—(C₃H₆O)_(e)—R′→R′—(C₃H₆O)_(e)—(C₂H₄O)_(f)—(CH₂)_(r-2)—CH₂CH₂—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—CH₂CH₂—(CH₂)_(r-2)—(C₂H—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂H+2CH₂═CH—(CH₂)_(r-2)—(C₃H₆O)₆—(C₂H₄O)_(f)—R→R—(C₂H₄O)_(e)—(C₃H₆O)_(f)—(CH₂)_(r-2)—CH₂CH₂—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂—CH₂CH₂—(CH₂)_(r-2)—(C₃H₆H—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂H+2CH₂═CH—CH₂—(CH₂)_(r-3)—(C₂H₄O)_(f)—(C₂H₄O)_(f)—(C₃H₆O)_(e)—R′→R′(C₃H₆O)_(e)(C₂H₄O)_(f)(CH₂)_(r-3)CH₂CH₂CH₂Si(CH₃)₂O(Si(CH₃)₂O)_(y)Si(CH₃)₂—CH₂CH₂CH₂(CH₂

which can also be written as

R′—(C₃H₆O)_(e)—(C₂H₄O)_(f)—(CH₂)_(s)—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂—(CH₂)_(s)—(C₂H₄O)_(f)—(C₃H₆O)_(e)—R′H—Si(CH₃)₂O—(Si(CH₃)₂O)_(y)—Si(CH₃)₂H+2CH₂═CH—CH₂—(CH₂)_(r-3)—(C₃H₆O)_(e)—(C₂H₄O)_(f)—R→R(C₂H₄O)_(f)(C₃H₆O)_(e)(CH₂)_(r-3)CH₂CH₂CH₂Si(CH₃)₂O(Si(CH₃)₂O)_(y)Si(CH₃)₂—CH₂CH₂CH₂(CH₂)_(r-3)(C₃H₆O)_(e)

which can also be written as

R—(C₂H₄O)_(f)—(C₃H₆O)_(e)—(CH₂)_(s)—Si(CH₃)₂—O—(Si(CH₃)₂—O)_(y)—Si(CH₃)₂—(CH₂)_(s)—(C₃H₆O)_(e)—(C₂H₄O)_(f)—R

wherein R, R′ and y are as defined hereinabove with respect to Formulae1, 2, 3, and 4, and e=i=l and f=z=p wherein i, l, z, and p are asdefined hereinabove with respect to Formulae 1, 2, 3, and 4, and r and sare integers.

The coupling reaction of a hydropolysiloxane derivative (containing≡SiH) and a hydroxyl active material (HOR) such as polyethylene glycol,polypropylene glycol, mixed polyethyleneglycol and polypropylene glycol,alkyl ethers of polyethylene glycol, alkyl ethers of polypropyleneglycol, alkyl ethers of mixed polyethyleneglycol and polypropyleneglycol, or the like in the presence of a metal catalyst is known. Thecoupling reaction of a polydimethylsiloxane derivative comprising twoactive terminal ≡SiH groups and an unsaturated material (with a doublebond, such as vinyl or ally group containing polyethyleneoxide,polypropyleneoxide, or mixture thereof) in the presence of a metalcatalyst is also known. Additional synthetic methods for the preparationof ABSCS′B′A′ and BASCS′A′B′ block copolymers for the inks of thepresent invention are disclosed in, for example, Silicon Compounds:Register and Review (5^(th) Edition), published by United ChemicalTechnologies, Inc. (Formally Hüls America, Inc. or Petrarch Systems,Inc., Bartram Road, Bristol, Pa. 19007), the disclosure of which istotally incorporated herein by reference.

The ABCBA or BACAB block copolymer is present in the ink of the presentinvention in any desired or effective amount, typically at least about0.001 percent by weight of the ink, preferably at least about 0.005percent by weight of the ink, and more preferably at least about 0.01percent by weight of the ink, and typically no more than about 8 percentby weight of the ink, preferably no more than about 5 percent by weightof the ink, and more preferably no more than about 4 percent by weightof the ink, although the amount can be outside of these ranges.

The inks of the present invention can optionally include a jetting aidsuch as polyethylene oxide (typically in amounts of less than about 5percent by weight) or a small quantity (typically less than about 0.2percent by weight) of stabilized pigment particles. A preferredpolyethylene oxide is one having a weight average molecular weight ofabout 18,500, although the molecular weight of the jetting aid can bedifferent. Examples of inks containing preferred polyethylene oxides aredisclosed in, for example, U.S. Pat. No. 5,207,825, the disclosure ofwhich is totally incorporated herein by reference. The jetting aidprovides smooth jetting or jetting with low jitter.

Other desired additives, including water soluble polymers, pH bufferingagents, biocides, chelating agents (EDTA and the like), anticurl agents,antibleed agents, and other known ink additives can also optionally beused in the inks of the present invention. Such additives can generallybe added to the inks in known amounts for their known purposes.

Additives such as surfactants (or wetting agents), anti-curl agents,anti-intercolor bleed agents, and anticlogging agents can also be addedto the inks of the present invention. Some of these surfactants can beof the anionic, cationic, or nonionic types. Suitable surfactants andwetting agents include, but are not limited to, Tamol SN®, Tamol LG®,and Triton® series (Rohm and Haas Co.); Marasperse® series; Igepal®series (Rhone-Poulenc Co., formerly from GAF Co.); Tergitol® series;Duponol® series (E. I. Du Pont de Nemours & Co.); Surfynol Series (AirProducts Inc.); Iconol® Series (BASF Co.); Brij® Series (ICI AmericasInc.); Pluronic® Series (BASF Co.); Emulphor® ON 870 and ON 877 (GAF);and other commercially available surfactants. These surfactants (ordispersants) and wetting agents can be present in the ink in effectiveamounts, generally from 0 to about 15 percent by weight of the ink,preferably from about 0.001 to about 10 percent by weight of the ink,and more preferably from about 0.01 to about 8 percent by weight of theink, although the amount can be outside of these ranges.

Polymeric additives can also be added to the inks for the presentinvention to enhance the viscosity or smear resistance of the ink.Suitable polymeric additives include, but are not limited to, watersoluble polymers and random copolymers such as Gum Arabic, salts,polyvinyl alcohols, polyvinyl sulfonate salts,polyhydroxypropylcellulose, polyhydroxyethylcellulose,polyvinylpyrrolidinone, polyvinylether, starch, polysaccharides,carboxymethylcellulose salts, polyethyleneimines derivatized withethylene oxide and/or propylene oxide, such as the Discole® series (DKSInternational); the Jeffamine® series (Texaco); and the like as well asmixtures thereof. Polymeric additives can be present in the ink inamounts of from 0 to about 10 percent by weight of the ink, preferablyfrom about 0.001 to about 8 percent by weight of the ink, and morepreferably from about 0.01 to about 5 percent by weight of the ink,although the amount can be outside of these ranges.

Other optional additives include, but are not limited to, biocides suchas Dowicil® 150, 200, and 75, benzoate salts, sorbate salts, Proxcel®(available from ICI), and the like. When used, such biocides aregenerally present in an amount of from 0 to about 10 percent by weightof the ink, preferably from about 0.001 to about 8 percent by weight ofthe ink, and more preferably from about 0.01 to about 4.0 percent byweight of the ink, although the amount can be outside of these ranges.Inks for the present invention can also include pH controlling(buffering) agents. Suitable pH controlling agents or buffering agentsinclude, but are not limited to, acids, bases, phosphate salts,carboxylate salts, sulfite salts, sulfate salts, amine salts, and thelike. Such pH controlling agents (buffering agents) are generallypresent in an amount of from 0 to about 10 percent by weight of the ink,preferably from about 0.001 to about 7.5 percent by weight of the ink,and more preferably from about 0.01 to about 5 percent by weight of theink, although the amount can be outside of these ranges.

The ink compositions can be of any desired or suitable viscosity. Forthermal ink jet printing applications, for example, the viscosity can beup to about 25 centipoise at about 25° C., preferably being below about10 centipoise at about 25° C., and more preferably being below about 5centipoise at about 25° C., although the viscosity can be outside theseranges, particularly for applications other than thermal ink jetprinting, such as acoustic ink jet printing or the like.

Inks of the present invention exhibit fast drying rates, low intercolorbleed, and reduced mottle and smearing. While not being limited to anyparticular theory, it is believed that the inks of the present inventionhave low surface tension that allows them to penetrate faster intoprinted substrate, thus preventing intercolor bleed. Printing a lowsurface tension ink (such as a color ink) underneath a high surfacetension ink (such as a black ink) can also enhance the drying rate ofthe black ink and reduce its intercolor bleed with the neighboring colorink. The ink comprising the BASCS′A′B′ or ABSCS′B′A′ block copolymer ofthe present invention can also provide a hydrophobic layer near theborder area next to its adjacent ink, thereby inhibiting intercolorbleed. In addition, since the inks of the present invention do not reactwith many common ink jet ingredients, they can be used in conjunctionwith many other ink compositions in a single partitioned printheadwithout resulting in undesired ink mixing, colorant precipitation, orprinthead clogging. The inks of the present invention can have lowsurface tension and can exhibit decreased dry time on print substrates.The inks of the present invention can also be printed under or aboveanother ink to enhance the drying rate of the other ink.

The present invention is also directed to a process which entailsincorporating an ink composition of the present invention into an inkjet printing apparatus and causing droplets of the ink composition to beejected in an imagewise pattern onto a print substrate. In oneparticularly preferred embodiment, the printing apparatus employs athermal ink jet process wherein the ink in the nozzles is selectivelyheated in an imagewise pattern according to digital signals, therebycausing droplets of the ink to be ejected in imagewise pattern onto theprint substrate. In another embodiment, the printing apparatus employsan acoustic ink jet process wherein droplets of the ink are ejected inimagewise pattern onto the print substrate by acoustic beams accordingto electronic signals. Optionally, the print substrate can be heated byany desired heating means at any stage of the ink jet printing process,including before printing, during printing, after printing, orcombinations thereof.

The print substrate employed can be any substrate compatible withaqueous inks. Suitable substrates include, but are not limited to,textiles; plain papers, such as Xerox® series 10, Xerox® 4024, Xerox®Digital Paper, Xerox® Image Series LX Paper, Hewlett-Packard®BrightWhite Ink Jet plain paper, Georgia Pacific® Microprint Ink Jetpaper 24 lb, Xerox® 4200 DP paper, Rank Xerox® Plain Paper, JapaneseHokuetsu L Plain Paper, Fuji Xerox® Kakusaku L paper, various Japaneseplain papers, Strathmore® Legacy paper, Ampad® Premium grade paper,Hammermill® Jet Print paper, Hammermill® Tidal DP paper, GP Microprintpaper, Weyerhaeuser® Jet-Xtra paper, Boise® Cascade paper, Union Camp®Great White Recycled paper, Union Camp® Top Gun ink jet paper, Champion®paper, commercial bond papers and the like; coated papers (or specialink jet papers including photo-realistic ink jet papers) such as thoseavailable from Hewlett-Packard, Canon, Eastman Kodak, Oji Paper, 3M,Mitsubishi, Polaroid, Lexmark, Epson, and Xerox; ink jet transparenciessuitable for aqueous inks or ink jet printing processes, including thosefrom Arkwright, Hewlett-Packard, Canon, Asahi, Lexmark, Epson, EastmanKodak, Polaroid, and Xerox; and the like, as well as materials fromother commercial sources.

Another embodiment of the present invention is directed to a set of inksfor printing multicolor images in an ink jet printer, said ink setcomprising (1) a first ink having a first color and comprising water anda first colorant; and (2) a second ink having a second color differentfrom the first color and comprising water, a second colorant, and anABSCS′B′A′ or BASCS′A′B′ block copolymer wherein A and A′ are blockscontaining one or more ethylene oxide repeat monomer units, B and B′ areblocks containing one or more propylene oxide repeat monomer units, C isa block comprising one or more repeat monomer units of adialkylsiloxane, alkyl aryl siloxane, or diarylsiloxane, S is anoptional spacer group between the A or B block and the C block, and S′is an optional spacer group between the C block and the A′ or B′ block,wherein dry time of the ink containing the block copolymer is decreasedand/or intercolor bleed between the first ink and the second ink isreduced when the first ink and the second ink are printed adjacent toeach other on a print substrate. Yet another embodiment of the presentinvention is directed to a multicolor ink jet printing process whichcomprises: (1) incorporating into an ink jet printer a first ink havinga first color and comprising water and a first colorant; (2)incorporating into the ink jet printer a second ink having a secondcolor different from the first color and comprising water, a secondcolorant, and an ABSCS′B′A′ or BASCS′A′B′ block copolymer wherein A andA′ are blocks containing one or more ethylene oxide repeat monomerunits, B and B′ are blocks containing one or more propylene oxide repeatmonomer units, C is a block comprising one or more repeat monomer unitsof a dialkylsiloxane, alkyl aryl siloxane, or diarylsiloxane, S is anoptional spacer group between the A or B block and the C block, and S′is an optional spacer group between the C block and the A′ or B′ block;(3) causing droplets of the first ink to be ejected in an imagewisepattern onto a substrate; and (4) causing droplets of the second ink tobe ejected in an imagewise pattern onto the substrate, wherein dry timeof the ink containing the block copolymer is decreased and/or intercolorbleed between the first ink and the second ink is reduced when the firstink and the second ink are printed adjacent to each other on thesubstrate. Still another embodiment of the present invention is directedto a multicolor ink jet printing process which comprises: (1)incorporating into an ink jet printer a first ink having a first colorand comprising water and a first colorant; (2) incorporating into theink jet printer a second ink having a second color different from thefirst color and comprising water, a second colorant, and an ABSCS′B′A′or BASCS′A′B′ block copolymer wherein A and A′ are blocks containing oneor more ethylene oxide repeat monomer units, B and B′ are blockscontaining one or more propylene oxide repeat monomer units, C is ablock comprising one or more repeat monomer units of a dialkylsiloxane,alkyl aryl siloxane, or diarylsiloxane, S is an optional spacer groupbetween the A or B block and the C block, and S′ is an optional spacergroup between the C block and the A′ or B′ block; (3) causing dropletsof the first ink to be ejected in an imagewise pattern onto a substrate;and (4) causing droplets of the second ink to be ejected in an imagewisepattern onto the substrate, wherein dry time of the first ink is reducedwhen the second ink is printed either above or below the first ink. Itis believed that the dry time of the first ink can be reduced by thepriming action of the second ink, which can have reduced surfacetension.

In a multicolor printing process, any ink printing order (such as (1)black, cyan, magenta, yellow, (2) yellow, cyan, magenta, black, (3)yellow, magenta, cyan, black, (4) black, magenta, yellow, cyan, or thelike can be used in the printing process. In particular, the inkcontaining the ABSCS′B′A′ or BASCS′A′B′ block copolymer can be printedonto the substrate either before or after the ink that contains noABSCS′B′A′ or BASCS′A′B′ block copolymer.

Specific embodiments of the invention will now be described in detail.These examples are intended to be illustrative, and the invention is notlimited to the materials, conditions, or process parameters set forth inthese embodiments. All parts and percentages are by weight unlessotherwise indicated.

EXAMPLE I

A black ink jet ink was prepared by simple mixing of the followingingredients: CABOJET® 300 carbon black dispersion (dispersion added inan amount such that the ink contained 3 percent by weight pigmentsolids; obtained from Cabot Corp.); sulfolane (20 percent by weight;obtained from Phillips Petroleum Co.); polyacrylamide (0.6 percent byweight; molecular weight about 5,000; obtained from Aldrich ChemicalCo.); polyethylene glycol (4 percent by weight; molecular weight about200; obtained from Aldrich Chemical Co.); polyethylene oxide (0.05percent by weight; average molecular weight about 18,500; obtained fromPolysciences); poly(dimethylsiloxane) ethoxylated, 3-hydroxypropoxylateend-capped (0.05 percent by weight; obtained from Aldrich Chemical Co.,48,271-4, CAS No. 68037-63-8); and the balance water. Thepoly(dimethylsiloxane) ethoxylated, 3-hydroxypropoxylate end-cappedpolymer is believed to be a BACA′B′ polymer of the formula

wherein the two terminal groups are hydroxyl, i and l are each 1, z=p,and the ratio of ethylene oxide (EO) to propylene oxide (PO) is 80:20.

EXAMPLE II

A yellow ink composition was prepared by simple mixing of the followingingredients followed by filtration through a Nylon membrane filter of0.8 micron:

Amount (parts by Ingredient Supplier weight) deionized water — 0.785DOWICIL ® 150/200 biocide Dow Chemical Co. 0.1 polyethylene oxide*Polysciences 0.05 imidazole BASF 1 ethylene diamine tetraacetic DowChemical Co. 0.065 acid urea Arcadian Corp. 6 sulfolane** PhillipsPetroleum Co. 15 acetylethanolamine*** Scher Chemical 16 butyl carbitolVan Waters & Rogers 12 PROJET ® YELLOW OAM Zeneca Colors 40 dye**** rollmill 30 minutes *average molecular weight 18,500 **95 wt. % sulfolane, 5wt. % water ***75 wt. % acetylethanolamine, 25 wt. % water****containing 7.5 wt. % Acid Yellow 23 dye in water

EXAMPLE III

The black ink prepared in Example I and the yellow ink prepared inExample II were incorporated into a Hewlett-Packard® 855C thermal inkjet printer and operated at room temperature in Auto/Portrait/Normalmodes to print images on various plain papers.

The Midrange Frequency Line Edge Noise (MFLEN), which is a way toevaluate line edge sharpness, was employed to evaluate line sharpness ofthe black line images (made with the ink of Example I) on differentplain papers. MFLEN values were measured to quantify line edgeraggedness for the black ink printed on various plain papers without aneighboring ink. The small MFLEN numbers indicate sharp image of theblack ink on various plain papers.

Intercolor bleed was also measured and evaluated as a MFLEN value.Intercolor bleed (ICB) usually is caused by undesirable mixing of inksnear the bordering areas and results in a distorted line image withirregular edges and large MFLEN values. The smaller intercolor bleedMFLEN number is desirable because it shows sharper line image withreduced intercolor bleed.

The MFLEN numbers were obtained by equipment comprising a personalcomputer, an illuminating light source, a filter, and an imagingmicroscope with a CDD sensor (light sensor). The equipment wascalibrated with a standard image (line with sharp edges). Software usinga Fourier Transform technique was used to calculate the MFLEN data andline width. The average MFLEN of the images made with the black ink ofExample I alone as well as the black ink next to the yellow ink(intercolor bleed (ICB) between the inks of Example I and Example II)are shown in the table below:

Paper MFLEN ICB MFLEN Fuji Xerox “S” thin copier paper 56 gsm 4.3 30.7Fuji Xerox MultiAce paper 63 gsm 11.3 26.3 Fuji Xerox “J” copier paperfor color copier 82 0.4 16.0 gsm Fuji Xerox WR100 (100% post wastepapers) 67 12.0 35.7 gsm Fuji Xerox Sankoku L paper 5.4 19.4 Fuji XeroxGreen 100 paper 2.6 24.1 Xerox Image Series LX 0.7 9.2 Hammermill TidalDP, International Paper, 14.9 19.2 Selma, AL Xerox Office Paper 75 gsm0.5 22.5 Average 5.8 22.6

The black ink of Example I (second ink in this case) was also used togenerate images on a number of papers, and the optical density of thegenerated images (absolute value with calibration of background) wasmeasured. The results were as follows:

Paper Image Optical Density Fuji Xerox “S” thin copier paper 56 gsm 1.47Fuji Xerox MultiAce paper 63 gsm 1.43 Fuji Xerox “J” copier paper forcolor 1.56 copier 82 gsm Fuji Xerox WR100 (100% post waste 1.44 papers)67 gsm Fuji Xerox Yamayuri paper 1.26 Fuji Xerox Sankoku L paper 1.43Fuji Xerox Green 100 paper 1.43 Fuji Xerox Hokuetsu L 1.50 Fuji XeroxKakusaku L 1.46 Xerox Image Series LX 1.46 (Hammermill Tidal DP,International 1.33 Paper, Selma, AL Xerox 4024 paper 1.44 Xerox Digitalpaper 75 gsm 3R70389 1.47 Xerox Elite Image 24 LB (High Tech Laser) 1.38Xerox High Tech Ink Jet 20 LB 1.48 XL Business 80 gsm 1.40 Fuji Xerox WR100 (100% post waste 1.38 papers) 67 gsm Xerox Office Paper 75 gsm 1.48Xerox Expressions 1.49 Average 1.44

EXAMPLE IV

A black ink was prepared by admixing 15.8 percent by weight sulfolane(obtained from Phillips Petroleum Co.; commercial product contained 95percent by weight sulfolane and 5 percent by weight water), 7.7 percentby weight 2-pyrrolidinone (obtained from Aldrich Chemical Co.;commercial product contained 95 percent by weight 2-pyrrolidinone and 5percent by weight water), 16.7 percent by weight Cab-O-Jet® IJX157carbon black dispersion (obtained from Cabot Corporation), and water(balance). The ink was filtered through a 1.0 micron glass filter. Thisink (a reference or control ink for Example V) had a surface tension of54.6 dynes per centimeter and a viscosity of 1.63 centipoise.

EXAMPLE V

A black ink was prepared by ad mixing 15.8 percent by weight sulfolane(obtained from Phillips Petroleum Co.; commercial product contained 95percent by weight sulfolane and 5 percent by weight water), 7.7 percentby weight 2-pyrrolidinone (obtained from Aldrich Chemical Co.;commercial product contained 95 percent by weight 2-pyrrolidinone and 5percent by weight water), 16.7 percent by weight Cab-O-Jet® IJX157carbon black dispersion (obtained from Cabot Corporation), 0.05 percentby weight poly(dimethylsiloxane) ethoxylated, hydroxypropoxylateend-capped (obtained from Aldrich Chemical Co., 48,271-4, CAS No.68037-63-8), and water (balance). The ink was filtered through a 1.0micron glass filter. The ink had a surface tension of 36 dynes percentimeter.

EXAMPLE VI

The black inks of Examples IV and V were incorporated into a Lexmark®7200 Thermal Ink Jet Printer and printed on various papers usingAuto/Normal mode. Dry time data were recorded for the inks of ExamplesIV and V (in seconds) and were as follows:

IV V Paper (seconds) (seconds) Fuji Xerox “S” thin copier paper 56 gsm108 35 Fuji Xerox MultiAce paper 63 gsm 33 26 Fuji Xerox “P” copierpaper 64 gsm 9 5 Fuji Xerox “J” copier paper for color copier 82 82 41gsm Fuji Xerox WR100 (100% post waste papers) 67 4 2.5 gsm Fuji XeroxYamayuri paper 28 23 Fuji Xerox Sankoku L paper 15 5 Fuji Xerox Green100 paper 13 8 Fuji Xerox Hokuetsu L 60 34 Japanese Sharp PPC paper 15878 Xerox High Tech Ink Jet, 20 lb. 50 24 Xerox Office Paper 75 gsm 30 11Xerox Xpressions paper 44 23 Xerox High Tech Laser 24 lb. 8.5 4.5 XLBusiness 80 gsm 2 1 Hammermill CopyPlus 20 lb. 10 8 Average 40.9 20.6

The results of dry time measurements indicate that the ink of Example Vcontaining the BASCS′A′B′ block copolymer according to the presentinvention dried significantly faster on different plain papers comparedto the control ink of Example IV. Solid area image uniformity was alsoqualitatively evaluated on these papers for the inks of Examples IV andV. The results were as follows:

Paper IV V Fuji Xerox “S” thin copier paper 56 gsm Bad OK Mottle FujiXerox MultiAce paper 63 gsm Slight OK Mottle Fuji Xerox “P” copier paper64 gsm OK OK Fuji Xerox “J” copier paper for color copier 82 Bad Slightgsm Mottle Mottle Fuji Xerox WR100 (100% post waste papers) 67 OK OK gsmFuji Xerox Yamayuri paper Bad Low Mottle Density Fuji Xerox Sankoku Lpaper Slight OK Mottle Fuji Xerox Green 100 paper Slight OK Mottle FujiXerox Hokuetsu L Slight OK Mottle Japanese Sharp PPC paper Bad SlightMottle Mottle Xerox High Tech Ink Jet, 20 lb. Bad OK Mottle Xerox OfficePaper 75 gsm Slight OK Mottle Xerox Xpressions paper Bad Slight MottleMottle Xerox High Tech Laser 24 lb. Slight OK Mottle XL Business 80 gsmSlight OK Mottle Hammermill CopyPlus 20 lb. Mottle Slight Mottle

As indicated, the ink of Example V containing the BASCS′A′B′ blockpolymer according to the present invention generated solid area imageswith reduced mottle and more uniform solid area images compared to thecontrol ink of Example IV.

EXAMPLE VII

The black inks of Examples IV and V were incorporated into a Lexmark®7200 Thermal Ink Jet Printer and printed on various papers usingAuto/Normal mode in both horizontal and vertical directions, alone andnext to the yellow ink prepared in Example II to evaluate edge sharpnessof the black lines alone and intercolor bleed (ICB) between the blackinks and their neighboring yellow ink. MFLEN values for the black inksalone in the horizontal (MFLEN (H)) and vertical (MFLEN (V)) directionswere as follows:

MFLEN MFLEN MFLEN MFLEN Paper (H) IV (H) V (V) IV (V) V HammermillCopyPlus 20 lb. 7.2 9.4 7.2 6.4 Xerox High Tech Laser 24 lb. 3 4.4 4.75.9 Xerox High Tech Ink Jet, 20 lb. 0.1 0.2 1.9 2.1 XL Business 80 gsm3R91820 2 4.4 4.3 5.1 Fuji Xerox WR100 (100% post 1.6 2.8 3.3 3.3 wastepapers) 67 gsm Xerox Office Paper 75 gsm 1 1.7 0.9 4.1 Xerox Xpressions1.1 1 1 .3 1.3 Hewlett-Packard Bright White 3.2 2.6 8.4 4.6 ink jetpaper IBM Premium paper 0.8 0.5 2.3 3.2 Average 2.2 3 3.8 4

Inks IV and V show very good line edge acuity with low MFLEN values.MFLEN values for the black inks printed next to the yellow ink in thehorizontal (ICB (H)) and vertical (ICB (V)) directions were as follows:

ICB (H) ICB (H) ICB (V) ICB (V) Paper IV V IV V Hammermill CopyPlus 20lb. 20.3 12.7 18.5 13.1 Xerox High Tech Laser 24 lb. 20.8 11.7 18.9 15.5Xerox High Tech Ink Jet, 20 lb. 8.2 9.3 10.9 10.4 XL Business 80 gsm3R91820 14.2 13.3 18.6 14.1 Fuji Xerox WR100 (100% post 21.1 14.3 29.317.8 waste papers) 67 gsm Xerox Xpressions 1.3 1.4 2.8 4.8Hewlett-Packard Bright White ink 7.3 5.7 8.3 7.1 jet paper IBM Premiumpaper 21.1 17.2 21 20.5 Average 14.3 10.7 16 12.9

The above results indicate that the control ink of Example IV and theink of Example V containing the BASCS′A′B′ block copolymer according tothe present invention gave similarly good MFLEN data in horizontal andvertical directions. For intercolor bleed in both horizontal andvertical directions, however, the ink of Example V containing theBASCS′A′B′ block copolymer according to the present invention gaveimproved average results compared to the control ink of Example IV.

EXAMPLE VIII

A cyan ink was prepared by admixing Acid Blue 9 dye (2.0 percent byweight), diethyleneglycol (0.2 percent by weight), trimethylopropropane(11.0 percent by weight), dipropyleneglycol (2.0 percent by weight), andwater (balance). This ink was used as a reference ink or control.

EXAMPLE IX

A cyan ink was prepared by admixing Acid Blue 9 dye (2.0 percent byweight), diethyleneglycol (0.2 percent by weight), trimethylopropropane(11.0 percent by weight), dipropyleneglycol (2.0 percent by weight), apoly(dimethylsiloxane) ethoxylated hydroxypropoxylate end-capped blockcopolymer (0.2 percent by weight; obtained from Aldrich Chemical Co.;CAS 68037-63-8), and water (balance). This ink according to the presentinvention dried on print substrates faster than the ink in Example VIII.

EXAMPLE X

A yellow ink was prepared by admixing 51.63 percent by weight ProjetYellow OAM dye solution (containing 7.5 percent by weight Acid Yellow 23dye), 14.4 percent by weight sulfolane (commercial product contained 95percent by weight sulfolane and 5 percent by weight water), 11.52percent by weight acetylethanolamine, 10 percent by weight butylcarbitol, 6 percent by weight urea, 0.96 percent by weight imidazole,0.096 percent by weight Dowicil® 150/200 biocide, 0.062 percent byweight EDTA, 0.048 percent by weight polyethyleneoxide (averagemolecular weight 18,500), and distilled water (balance). The ink wasfiltered through a 1.2 micron Nylon membrane filter. This ink was usedas a reference ink or control.

EXAMPLE XI

A yellow ink was prepared by admixing 51.63 percent by weight ProjetYellow OAM dye solution (containing 7.5 percent by weight Acid Yellow 23dye), 14.4 percent by weight sulfolane (commercial product contained 95percent by weight sulfolane and 5 percent by weight water), 11.52percent by weight acetylethanolamine, 10 percent by weight butylcarbitol, 6 percent by weight urea, 0.96 percent by weight imidazole,0.096 percent by weight Dowicil® 150/200 biocide, 0.062 percent byweight EDTA, 0.048 percent by weight polyethyleneoxide (averagemolecular weight 18,500), 0.15 percent by weight poly(dimethylsiloxane)ethoxylated hydroxypropoxylate end-capped (CAS 68037-63-8), anddistilled water (balance). The ink was filtered through a 1.2 micronNylon membrane filter. This ink dried on print substrates faster thanthe ink in Example X.

Other embodiments and modifications of the present invention may occurto those of ordinary skill in the art subsequent to a review of theinformation presented herein; these embodiments and modifications, aswell as equivalents thereof, are also included within the scope of thisinvention.

What is claimed is:
 1. An ink composition comprising water, a colorant,and an ABSCS′B′A′ or BASCS′A′B′ block copolymer wherein A and A′ areblocks containing one or more ethylene oxide repeat monomer units, B andB′ are blocks containing one or more propylene oxide repeat monomerunits, C is a block comprising one or more repeat monomer units of anmonoalkylsiloxane, an alkyl aryl siloxane, or a diarylsiloxane, S is anoplional spacer group between the A or B block and the C block, and S isan oplional spacer group between the C block and the A′ or B′ block,wherein the block copolymer is of the formula

wherein R and R′ each, independently of the other, are hydrogen atoms,hydroxyl groups, alkyl groups, hydroxyl-substituted alkyl groups, oralkoxy groups, R₁ and R₂ each, independently of the other, is a hydrogenatom, an alkyl group, or an aryl group with the proviso that R₁ and R₂cannot both simultaneously be alkyl groups, whether the same ordifferent, z, i, l, and p are each integers representing the numbers ofrepeat alkylene oxide monomer units, wherein z, i, l, and p are each,independently of the other, from 1 to about 10,000, y is an integerrepresenting the number of repeat siloxane monomer units and is from 1to about 5,000, and j and k are each integers representing the number ofrepeat —(CH₂)— units and are each, independently of the other, from 1 toabout 10, wherein j+k≧1.
 2. An ink composition according to claim 1wherein the S and S′ optional spacer groups each, independently of theother, are methylene, ethylene, propylene, or mixtures thereof.
 3. Anink composition according to claim 1 wherein R and R′ each,independently of the other, are hydrogen atoms, alkyl groups with from 1to about 30 carbon atoms, hydroxyl-substituted alkyl groups with from 1to about 30 carbon atoms, or alkoxy groups with from 1 to about 30carbon atoms, R₁ and R₂ each, independently of the other, is a hydrogenatom, an alkyl group with from 1 to about 10 carbon atoms, or an arylgroup with from 6 to about 20 carbon atoms with the proviso that R₁ andR₂ cannot both simultaneously be alkyl groups, whether the same ordifferent, i, z, p, and l each, independently of the others, areintegers of from 1 to about 10,000, and y is an integer of from 1 toabout 5,000.
 4. An ink composition according to claim 1 wherein theblock copolymer is of the formula


5. An ink composition according to claim 1 wherein the block copolymeris present in the ink in an amount of at least about 0.001 percent byweight of the ink and wherein the block copolymer is present in the inkin an amount of no more than about 8 percent by weight of the ink.
 6. Anink composition according to claim 1 wherein the colorant is a dye. 7.An ink composition according to claim 1 wherein the colorant is apigment.
 8. An ink jet printing process which comprises incorporatinginto an ink jet printing apparatus an ink composition according to claim1 and causing droplets of the ink composition to be ejected in animagewise pattern onto a print substrate.
 9. An ink jet printing processaccording to claim 8 wherein the printing apparatus employs a thermalink jet printing process wherein the ink in the nobles is selectivelyheated in an imagewise pattern according to digital signals, therebycausing droplets of the ink to be ejected in imagewise pattern onto theprint substrate.
 10. An ink jet printing process according to claim 8wherein the printing apparatus employs a piezoelectric ink jet printingprocess.
 11. An ink jet printing process according to claim 8 whereinthe printing apparatus employs an acoustic ink jet printing processwherein droplets of the ink are caused to be ejected in imagewisepattern onto the print substrate by acoustic beams.
 12. A set of inksfor printing multicolor images in an ink jet printer, said ink setcomprising (1) a first ink having a first color and comprising water anda first colorant; and (2) a second ink having a second color differentfrom the first color and comprising water, a second colorant, and anABSCS′B′A′ or BASCS′A′B′ block copolymer wherein A and A′ are blockscontaining one or more ethylene oxide repeat monomer units, B and B′ areblocks containing one or more propylene oxide repeat monomer units, C isa block comprising one or more repeat monomer units of anmonoalkylsiloxane, an alkyl aryl siloxane, or a diarylsiloxane, S is anoptional spacer group between the A or B block and the C block, and S′is an optional spacer group between the C block and the A′ or B′ block,wherein the block copolymer is of the formula

wherein R and R′ each, independently of the other, ore hydrogen atoms,hydroxyl groups, alkyl groups, hydroxyl-substituted alkyl groups, oralkoxy groups, R₁ and R₂ each, independently of the other, is a hydrogenatom, an alkyl group, or an aryl group with the proviso that R₁ and R₂cannot both simultaneously be alkyl groups, whether the same ordifferent, z, i, l and p are each integers representing the numbers ofrepeat alkylene oxide monomer units, wherein z, i, l, and p are each,independently of the other, from 1 to about 10,000, y is an integerrepresenting the number of repeat siloxane monomer units and is from 1to about 5,000, and j and k are each integers representing the number ofrepeat —(CH₂)— units and are each, independently of the other, from 1 toabout 10, wherein j+k≧1, wherein dry time of the ink containing theblock copolymer is decreased and/or intercolor bleed between the firstink and the second ink is reduced when the second ink is printedadjacent to, on top of, or underneath the first ink on a printsubstrate.
 13. A multicolor ink jet printing process which comprises:(1) incorporaiing into an ink jet printer a first ink having a firstcolor and comprising water and a first colorant; (2) incorporating intothe ink jet printer a second ink having a second color different fromthe first color and comprising water, a second colorant, and anABSCS′B′A′ or BASCS′A′B′ block copolymer wherein A and A′ are blockscontaining one or more ethylene oxide repeat monomer units, B and B′ areblocks containing one or more propylene oxide repeat monomer units, C isa block comprising one or more repeat monomer units ofmonoalkylsiloxane, an, or a diarylsiloxane, S is an optional spacergroup between the A or B block and the C block, and S′ is an optionalspacer group between the C block and the A′ or B′ block, wherein theblock copolymer is of the formula

wherein R and R′ each, independently of the other, are hydrogen atoms,hydroxyl groups, alkyl groups, hydroxyl-substituted alkyl groups, oralkoxy groups, R₁ and R₂ each, independently of the other, is a hydrogenatom, an alkyl group, or an aryl group with the proviso that R₁ and R₂cannot both simultaneously be alkyl groups, whether the same ordifferent, z, i, l, and p are each integers represenling the numbers ofrepeat alkylene oxide monomer units, wherein z, i, l, and p are each,independently of the other, from 1 to about 10,000, y is an integerrepresenting the number of repeat siloxane monomer units and is from 1to about 5,000, and j and k are each integers representing the number ofrepeat —(CH₂)— units and are each, independently of the other, from 1 toabout 10, wherein j+k≧1; (3) causing droplets of the first ink to beejected in an imagewise pattern onto a substrate; and (4) causingdroplets of the second ink to be ejected in an imagewise pattern ontothe substrate, wherein dry time of the ink containing the blockcopoiymer is decreased and/or intercolor bleed between the first ink andthe second ink is reduced when the second ink is printed adjacent to, ontop of, or underneath the first ink on the substrate.